Precision at the nanoscale: an ‘ionic’ view of composition, structure and properties

Abstract

The study of matter at the nanoscale has traditionally relied on electron microscopy and optical spectroscopy to relate particle size with emerging properties. Mass spectrometry (MS), although a century-old analytical technique, has emerged in recent decades as a central tool for investigating atomically precise clusters (APCs). The introduction of soft ionisation methods, such as electrospray ionisation (ESI) and matrix-assisted laser desorption/ionisation (MALDI), has enabled the detailed analysis of cluster composition, fragmentation pathways, and structural features of APCs. The integration of ion mobility spectrometry with MS has further allowed direct correlations among their molecular formula, structure, and stability. At the same time, new developments such as charge-detection MS, ultraviolet photodissociation, and mass photometry have expanded the analytical range to larger and more complex systems. Beyond fundamental characterisation, MS is increasingly being applied to probe intrinsic properties such as ionisation potentials and support material applications through cluster deposition and related approaches. This review highlights the expanding role of MS in APC research and the impact of mass spectrometry-based techniques in materials science.

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Anagha Jose

Anagha Jose received her BSc from the University of Calicut and M.Sc. from Cochin University of Science and Technology (CUSAT). She is currently a PhD scholar at the Indian Institute of Technology Madras (IITM) under the guidance of Prof. Thalappil Pradeep. She has been awarded the Prime Minister's Research Fellowship (PMRF). Her research interests include mass spectrometry of nanoclusters and nanoparticles, as well as the applications of atomically precise metal clusters.

B. S. Sooraj

B. S. Sooraj received a BS-MS Dual Degree from the Indian Institute of Science Education and Research Bhopal (IISERB) in 2019. He is currently a PhD scholar at the Indian Institute of Technology Madras (IITM) under the guidance of Prof. Thalappil Pradeep. He is a recipient of the prestigious Shyama Prasad Mukherjee (SPM) Fellowship. His research interests include atomically precise metal clusters, mass spectrometry of megadalton clusters and nanoparticles, and CryoEM-based single-particle reconstruction of nanoparticles.

Thalappil Pradeep

Thalappil Pradeep is an Institute Professor and Deepak Parekh Institute Chair Professor at the Indian Institute of Technology Madras (IITM), Chennai, India. His research interests are in molecular and nanoscale materials. He has authored 600 scientific papers, 10 books, 100+ Indian and 29 US/PCT patents, co-founded 7 start-ups and founded the International Centre for Clean Water (https://iccw.world). He is involved in the development of affordable technologies for drinking water purification. His pesticide removal technology has reached >10 million people. His arsenic removal technology, approved for national implementation, is delivering arsenic-free water to >1.4 million people every day. He is a recipient of the Shanti Swaroop Bhatnagar Prize, The World Academy of Sciences (TWAS) prize, Padma Shri, Nikkei Asia Prize, Prince Sultan Bin Abdulaziz International Prize for Water, VinFuture Prize and ENI award. He is a Fellow of all the science and engineering academies of India, TWAS, American Association for the Advancement of Science, African Academy of Sciences, US National Academy of Engineering and Academia Europaea. He has received the Lifetime Achievement Research Award of IITM and Distinguished Alumnus Award of Indian Institute of Science. As part of philanthropy, he supports a school in his village where 500 students are enrolled.

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1. Introduction

As John Fenn stated in his Nobel lecture, “Electrospray: Wings for Molecular Elephants”,¹ the technique has evolved, ‘from flames to flying elephants.’ What once seemed an improbable task, namely, transferring large biomolecules such as proteins and polymers into their gaseous phase, became possible through electrospray ionisation, a development that transformed modern mass spectrometry. This development has great consequence to cluster science as well.

The origin of mass spectrometry dates to the early 20^th century, when Sir J. J. Thomson constructed the first mass spectrograph,^2,3 then referred to as a “parabola spectrograph”, to measure the mass-to-charge (m/z) ratio of gaseous ions. His pioneering work not only led to the development of MS as an analytical technique but also provided the first evidence of isotopes. Francis W. Aston further expanded this observation and discovered isotopes in elements, for which he was awarded the Nobel Prize in Chemistry in 1922.⁴ In the early decades, MS was widely used in organic chemistry, primarily for the analysis of small molecules. Ionisation methods such as electron impact (EI) and electric discharge were well-suited for volatile and thermally stable compounds. As this field evolved, the utility of MS expanded to include more complex analytes such as sugars, alkaloids, and peptides.⁵ The development of hyphenated techniques, especially gas chromatography-mass spectrometry (GC–MS), significantly enhanced the ability to resolve and identify components in complex mixtures, establishing MS as an inevitable tool in analytical chemistry.^6,7

However, the expansion of MS into the realm of biomolecular analysis posed new challenges due to the fragility and high mass of proteins and nucleic acids. To address this, high-resolution double-focusing mass spectrometers were developed, as demonstrated by Todd, McGilvery, and Baldwin.⁸ These instruments enabled more accurate m/z measurements and facilitated early tandem MS (also designated as MS/MS) experiments for structural elucidation. However, the lack of efficient and non-destructive ionisation methods limited the analysis of large biomolecules.

A major paradigm shift occurred in the late 1980s with the introduction of soft ionisation techniques, notably electrospray ionisation (ESI)⁹ and matrix-assisted laser desorption ionisation (MALDI).^10,11 These techniques enabled the ionisation of large, fragile molecules under mild conditions, preserving their molecular integrity and allowing their introduction into the gas phase for mass analysis.¹² These breakthroughs had a profound impact, particularly in proteomics and macromolecular research, and their significance was recognised with the 2002 Nobel Prize in Chemistry awarded to John Fenn for electrospray ionisation (ESI) and Koichi Tanaka for soft laser desorption.¹³ These historical milestones reflect the continuous innovation in mass spectrometry that has expanded its analytical capabilities from elemental and isotopic analysis to the structural and compositional characterisation of large and complex molecular assemblies.

Atomically precise clusters (APCs), composed of tens to thousands of metal atoms stabilised by ligands and with core sizes below 3 nm, bridge the gap between atoms and bulk. Their closely spaced electronic orbitals give rise to multiple electronic transitions, photoluminescence, chirality, conductivity, and magnetism, distinguishing them from bulk metals.^14–17 Over 700 atomically precise clusters with nuclearities ranging from 2 to 2000 atoms have been reported,¹⁸ with more than 350 being structurally characterised by crystallography,¹⁹ including metals such as Au, Ag, Pt, and Cu, as well as their alloys. Conventional characterisation methods, such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and dynamic light scattering (DLS), often lack the resolution to fully capture the precise size and composition of these clusters.²⁰ However, MS offers capabilities that surpass conventional techniques, which make it an indispensable analytical tool in the analysis of APCs. Although electron microscopy and optical methods primarily provide information on morphology and size-dependent properties, MS enables the direct and accurate determination of cluster composition, isotopic distribution, charge states, and ligand architecture at the molecular level. It enables in-depth analysis of both bare and ligand-protected NCs, helping to understand their reactivity, transformation pathways, and gas-phase structures. MS/MS involves the analysis of mass-selected ions, which provides further insights into their structural features and fragmentation behaviour. Additionally, ion mobility mass spectrometry (IM-MS) enables the exploration of structural isomerism and conformational changes in the gas phase. Emerging techniques, including charge detection mass spectrometry (CDMS) and mass photometry (MP), are expanding the capabilities of MS by enabling single-particle sensitivity and accurate mass measurements for large, heterogeneous, or weakly ionising NCs.²¹

With the advancement of mass spectrometric (MS) instrumentation, recent developments have significantly expanded the analytical window in terms of accessible mass range, resolution and detection limit. Techniques such as Fourier transform ion cyclotron resonance (FT-ICR)^22,23 and Orbitrap mass spectrometry^24,25 now achieve resolutions above 1 000 000 and 500 000, respectively, with sub-femtomole sensitivity, enabling the accurate characterisation of molecules from small ions to multi-megadalton assemblies. Time-of-flight (TOF) and quadrupole-TOF (Q-TOF) analysers provide rapid acquisition and high-throughput analysis with resolutions approaching 100 000, making them valuable for complex biological and chemical systems.^26,27 CDMS and Orbitrap-CDMS extend measurements to the megadalton and gigadalton scales by directly determining the charge and mass of single ions with near unit-charge accuracy.^28,29 Mass photometry complements these approaches by offering label-free, single-particle mass analysis in solutions across the 30 kDa–10 MDa range.³⁰ Collectively, these developments provide powerful and versatile tools for high-resolution and high-sensitivity analysis in chemistry, biology, and materials science.

In addition to structural and compositional analysis, MS has enabled the real-time monitoring of cluster growth, ligand exchange, redox behaviour, and intermediate species during synthesis. The resemblance of NCs to biomolecules in terms of mass range and surface ligand environment makes ESI-MS particularly suited to their analysis, such as protein characterisation. Furthermore, the ability of MS to resolve complex mixtures and detect species with varying charge states expands its utility to very large NCs and even small nanoparticles with emerging surface plasmon resonance (e.g., Au₂₇₉(TBBT)₈₄ and Ag₁₄₆Br₂(TIBT)₈₀).^31,32 Complementary to MS, mass photometry enables the label-free, solution-phase quantification of the aggregation states and supramolecular assemblies of atomically precise clusters at the single-particle level.³³

Collectively, advancements in MS instrumentation and methodologies have firmly established both ESI and MALDI as indispensable platforms for the molecular-level characterisation of metal NCs.^34,35 They provide accurate data that is in strong agreement with the crystallographically and theoretically predicted structures, and thereby play a crucial role in the rational design of nanocluster-based materials. The field of mass spectrometry of APCs has expanded significantly over the years, with the research output now exceeding 700 publications (Fig. 1), indicating the rapidly growing interest and suggesting a surge in research efforts in this direction soon.

Fig. 1 Number of papers published each year on nanoclusters and mass spectrometry (collected from Web of Science using the keywords “nanoclusters”, “metal clusters”, “mass spectrometry” and “mass”). The data were collected up to July 31, 2025.

Mass spectrometry (MS), along with its advanced and hyphenated variants, has become a cornerstone in the characterisation of nanoclusters, providing unparalleled insights into their composition, structure, and dynamics.^35–38 In this review, we discuss the recent advances in MS-based approaches for studying atomically precise nanoclusters (APCs), with a focus on four key aspects including composition,³⁹ structure,⁴⁰ properties,⁴¹ and applications^42,43 (Fig. 2).

Fig. 2 Schematic depicting the role of mass spectrometry in atomically precise clusters (APCs), enabling a detailed understanding of their composition, structure, properties, and applications. Images under composition are adapted with permission from ref. 39. Copyright 2018, the American Chemical Society. Images under structure are adapted from ref. 40. Copyright 2017, the American Chemical Society. Images under properties are adapted from ref. 41. Copyright 2022, the American Chemical Society. Images under applications are adapted from ref. 42 and 43. Copyright 2011, the American Chemical Society and Copyright 2018, John Wiley and Sons, respectively.

2. Mass spectrometry: the gateway to nanoparticle characterisation

2.1. Composition of clusters

Since the 1980s, advancements in ionisation sources such as supersonic expansion and laser desorption ionisation (LDI) have established MS as a critical technique for characterising gas-phase metal clusters,^44,45 fullerenes,⁴⁶ and semiconductor clusters.^47,48 In 1994, Brust et al. made a breakthrough in the synthesis of thiol-protected gold nanoparticles (<3 nm),⁴⁹ which enabled the preparation of monodisperse, atomically precise nanoclusters, leading to extensive research in this area.

MS has rapidly emerged as an indispensable tool for determining the composition of noble metal nanoclusters, particularly gold (Au), silver (Ag), and platinum (Pt) nanoclusters. The early work by Murray and Whetten employed LDI-MS to analyse thiolate-protected gold nanoclusters, which initiated the use of MS in cluster science.^50–52 However, LDI, being a relatively harsh ionisation method, often caused fragmentation, limiting its utility for accurate molecular composition analysis. This challenge led to the adoption of softer ionisation techniques such as matrix-assisted laser desorption ionisation (MALDI) and electrospray ionisation (ESI), which allowed the detection of intact ligand-protected clusters. ESI-MS, in particular, has proven highly effective due to its gentle ionisation process, enabling the high-resolution detection of intact molecular ions, accurate charge-state determination, and precise elemental composition, which is crucial for structural elucidation. A notable example includes the identification of a 10.4 kDa glutathione-protected gold cluster, initially reported as Au₂₈(SG)₁₆ by Schaaff et al. in 1998 using MALDI and ESI-MS,⁵³ and later reassigned as Au₂₅(SG)₁₈ by Negishi et al. in 2005.⁵⁴ These advances have significantly deepened the molecular-level understanding of the structure and composition of gold nanoclusters.⁵⁵

At present, ESI-MS and MALDI-MS have become predominant analytical tools to precisely characterise the composition of ligand-protected metal nanoclusters. Numerous atomically precise gold NCs, including [Au₂₄(SAdm)₁₆] (Fig. 3a),⁵⁶ [Au₂₅(PET)₁₈],^57,58 and [Au₃₂(SC₂H₄Ph)₂₄] (Fig. 3b),⁵⁹ have been successfully characterised by ESI-MS, where the experimentally observed charge states and molecular weights closely match the crystallographic data, validating the cluster formulae with atomic-level accuracy. Although silver nanoclusters present analytical challenges due to their dual isotopes (¹⁰⁷Ag and ¹⁰⁹Ag) and lower stability, these issues have been effectively addressed by ESI-MS. The broader isotopic envelopes observed (e.g., Ag₂₅(DMBT)₁₈)⁶⁰ allow clear differentiation from their gold counterparts. ESI-MS has precisely identified nanoclusters such as [Ag₁₄₁X₁₂(S-Adm)₄₀]⁶¹ and Ag₆₇(SPhMe₂)₃₂(PPh₃)₈ (Fig. 3c),⁶² confirming both their 3+ charge state and molecular formula, in excellent agreement with their crystal structures. To improve the ionisation efficiency, especially for clusters with low intrinsic ionizability, ionisation enhancers such as caesium acetate (CsOAc)^63,64 are utilised, facilitating the formation of intact molecular ions. MALDI-MS, enhanced with optimised matrices such as DCTB (trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene] malononitrile), is widely used to analyse larger nanoclusters (e.g., Au₁₃₃(SPh-^tBu)₅₂ and Au₃₂₉(SCH₂CH₂Ph)₈₄),^65–67 often yielding intact molecular ion peaks with minimal fragmentation. MS has been extended beyond noble metals to non-noble metal clusters, heterometallic nanoclusters, and other ligand types. These clusters include metals such as Fe, Co, Ni, Cu, and Ir, as well as ligands such as hydrides, carboranes, carbenes, phosphines, and alkynyls. For example, [Ag₁₈H₁₆(TPP)₁₀], [Ag₂₅H₂₂(DPPE)₈],⁶⁸ Ag₄₀(C₂B₁₀H₁₀S₂)₁₂(PPh₃)₈,⁶⁹ Ag₆₁(dpa)₂₇(SbF₆)₄,⁷⁰ Ag₇₄(C≡CPh)₄₄,⁷¹ [Au₁₃(NHC)₅Cl₂]Cl₃,⁷² [Au₂₀(dppp₃)₄]Cl₄,⁷³ Au₂₂(C≡CPh)₁₈,⁷⁴ Au₁₁₀(C≡CC₃H₆Ph)₄₈,⁷⁵ Cu₁₈(PET)₁₆(PPh₃)₄Cl,⁷⁶ Cu₃₃H₁₈(Medpf)₁₂,⁷⁷ Cu₇₅(S-Adm)₃₂,⁷⁸ Pd₂₁(SCH₂CH₂Ph)₁₈,⁷⁹ Pt₈(C₂H₂O₂S)₈,⁸⁰ [Fe₅₅H₄₆(PtBu₃)₁₂]⁸¹ and [Ir₉(PET)₆].⁸²

Fig. 3 ESI-MS of (a) Au₂₄(SAdm)₁₆, (b) Au₃₂(SC₂H₄Ph)₂₄, (c) Ag₆₇(SPhMe₂)₃₂(PPh₃)₂, (d) Ag₁Ag₂₈(SR)₁₈(PPh₃)₄, (e) Au₁Ag₂₈(SR)₁₈(PPh₃)₄, (f) Pt₁Ag₂₈(SR)₁₈(PPh₃)₄, and (g) Pd₁Ag₂₈(SR)₁₈(PPh₃)₄. Simulated and experimental isotopic distributions are shown in the inset. Reproduced with permission from (a) ref. 56, (b) ref. 59, (c) ref. 62, (d) ref. 85, (e) ref. 85, (f) ref. 85 and (g) ref. 85. Copyright 2014, the American Chemical Society. Copyright 2021, John Wiley and Sons. Copyright 2016, the American Chemical Society. Copyright 2019, National Academy of Sciences.

ESI-MS confirmed the molecular composition and the fact that Au₄₄(2,4-DMBT)₂₆ was charge-neutral prior to ionisation by identifying the [Au₄₄(2,4-DMBT)₂₆ + 2Cs]²⁺ ion at m/z 6250.3. The observed 2+ charge state, arising from the addition of Cs⁺, supported the neutral nature of the cluster, in agreement with X-ray crystallography and XPS data.⁸³ In bimetallic systems, such as the Au₂₇Cd₁(SAdm)₁₄(DPPF)Cl nanocluster, both ESI-MS and MALDI-MS played complementary roles, where ESI-MS determined the precise molecular formula, while MALDI-MS helped identify surface ligands, supporting the structural data obtained from single-crystal X-ray diffraction.⁸⁴ Kang et al. constructed a comprehensive library of 21 atomically precise M₂₉ nanoclusters, ranging from monometallic to tetrametallic compositions, using a novel M₂₉(S-Adm)₁₈(PPh₃)₄ template. ESI-MS was pivotal in confirming the exact compositions and uniformity of these clusters, revealing single, intense peaks for each species (Fig. 3d–g). The charge states were identified as 3+ for Ag₂₉ and Au₁Ag₂₈, and 2+ for Pt₁Ag₂₈ and Pd₁Ag₂₈, which helped to establish their electronic configurations.⁸⁵ Zhu and coworkers utilised ESI-MS to confirm the atomic precision in the site-specific doping of Au₂₅(SR)₁₈ clusters, resolving single-atom substitutions and tracking the doping reversibility.⁸⁶ Similarly, Bootharaju et al. employed ESI-MS to verify single-atom gold doping in [Ag₂₄Au(SR)₁₈] clusters.⁸⁷ Soldan et al. quantified the gold doping levels in Ag₂₉(BDT)₁₂(TPP)₄, detecting up to five Au dopants (with minor populations of six and seven) through characteristic m/z shifts of 30 per substitution.⁸⁸

Overall, MS, particularly ESI-MS, is a critical technique for confirming the composition, charge, stoichiometry, and atomic-level doping of metal nanoclusters. It offers an unparalleled molecular-level understanding that complements crystallographic and spectroscopic methods.

2.2. Mass spectrometric insights into ligand-induced transformation

MALDI-MS and ESI-MS have been extensively used in elucidating the mechanistic details of ligand exchange-induced structural transformation (LEIST) in atomically precise nanoclusters by providing molecular-level insights into both the intermediate and final species.⁸⁹

Amala Dass and coworkers monitored the time-dependent core transformation in Au₁₄₄(SCH₂CH₂Ph)₆₀ using MALDI-MS. In the initial 2 h, they identified a new peak for Au₁₃₃(SPh-tBu)₅₂, and further they detected subsequent species such as Au₁₀₂(SPh-tBu)₄₄ and Au₂₇₉(SPh-tBu)₈₄ (Fig. 4a). However, due to its greater fragmentation, MALDI-MS failed to detect key intermediates such as Au₁₉₁(SPh-tBu)₆₆. This limitation was overcome by ESI-MS, which through softer ionisation, successfully identified Au₁₉₁(SPh-tBu)₆₆via its +2 and +3 charge states and Cs⁺ adducts (Fig. 4b). ESI-MS further confirmed the disappearance of Au₁₃₃ at 14 h, indicating its full conversion, and revealed the presence of intermediate-sized clusters (Au_98–104) that were not seen clearly by MALDI-MS. ESI-MS confirmed the purity of Au₁₄₄(PET)₆₀ and detected trace amounts of larger polydisperse species at later stages, suggesting cluster growth beyond Au₂₇₉.⁹⁰ Similarly, ESI-MS and optical spectroscopy were used to monitor the ligand-induced transformation of Au₃₈(PET)₂₄ to Au₃₆(TBBT)₂₄ (Fig. 4c). The reaction proceeds through four stages, i.e. ligand exchange, structural distortion, disproportionation to Au₃₆ and Au₄₀, and size focusing that yields Au₃₆(TBBT)₂₄ in ∼90% yield.⁹¹ Liu et al. successfully developed a synthetic protocol combining ligand exchange and size focusing. MALDI-MS revealed broad initial polydispersity centred around m/z ∼ 25 000, while the final product was confirmed as a single, well-defined Au₉₉(SPh)₄₂ nanocluster at m/z ∼ 24 000.⁹² Nimmala et al. describe the ligand-induced transformation of Au₁₄₄(SCH₂CH₂Ph)₆₀ into Au₁₃₃(SPh-tBu)₅₂ upon treatment with excess tert-butylbenzenethiol. ESI-MS precisely characterised the molecular compositions of both the starting and product clusters, capturing mixed-ligand intermediates such as Au₁₄₄(SCH₂CH₂Ph)_60−x(SPh-tBu)_x. The core-size conversion begins after ∼22 ligand substitutions, with Au₁₄₄(SCH₂CH₂Ph)₃₈(SPh-tBu)₂₂ showing enhanced stability. The detailed time-dependent mass spectral data (Fig. 4d) further revealed a stepwise evolution through intermediate-sized clusters (e.g., Au₁₃₇–Au₁₃₉) with varying ligand compositions, providing mechanistic insights into the ligand-exchange-induced structural rearrangements.⁹³

Fig. 4 (a) Schematic of the transformation of Au₁₄₄(SCH₂CH₂Ph)₆₀, and MALDI-MS of the starting Au₁₄₄(SCH₂CH₂Ph)₆₀ and its transformation to Au₁₃₃(SPh-tBu)₅₂, Au₁₉₁(SPh-tBu)₆₆, and Au₂₇₉(SPh-tBu)₈₄ upon reacting with 4-tert-butylbenzenethiol ligand at ∼140 °C for 14 h. (b) ESI-MS of the starting Au₁₄₄(SCH₂CH₂Ph)₆₀ at 0 h and its transformation to Au₁₃₃(SPh-tBu)₅₂, Au₁₉₁(SPh-tBu)₆₆, and Au₂₇₉(SPh-tBu)₈₄ upon reacting with 4-tert-butylbenzenethiol ligand at ∼140 °C for 14 h. (c) Time-dependent ESI-MS of the transformation reaction of Au₃₈ to Au₃₆ and corresponding UV–vis spectra of different times in parallel with ESI-MS. (d) Core size conversion of Au₁₄₄(SCH₂CH₂Ph)₆₀ to Au₁₃₃(SPh-tBu)₅₂ by ESI-MS. Adapted from (a) ref. 90, (b) ref. 90, (c) ref. 91 and (d) ref. 93. Copyright 2021, the American Chemical Society. Copyright 2013, the American Chemical Society. Copyright 2015, the American Chemical Society.

Collectively, MALDI-MS and ESI-MS facilitated a comprehensive understanding of the ligand-induced core transformations of clusters and the identification of intermediate species and final products, thereby providing insights into the mechanisms.

2.3. Atomic-scale insights into high-nuclearity nanoclusters

In 2014, Kumara et al. reported the synthesis and precise characterization of ‘Faradaurate-500’ (Au₅₀₀(SR)₁₂₀), a highly stable and monodisperse plasmonic gold nanocrystal with a diameter of approximately 2.4 nm, using ESI-MS and MALDI (Fig. 5a). Through analysis of multiply charged ions and ligand exchange experiments, they determined its molecular mass (115 kDa) and ligand number (120), achieving atomic-level compositional control rarely attained at this size.⁹⁴ Building on this, Dass and coworkers synthesised a larger gold thiolate cluster, ‘Faradaurate-940’(Au₉₄₀(SR)₁₆₀), the largest cluster characterised by ESI-MS to date. They combined ESI-MS and MALDI-MS to determine its molecular mass, which is 207.5 kDa, and confirmed the ligand count (160) by comparing nanoclusters synthesised with two different thiols, hexanethiol and phenylethanethiol. The gold atom number (∼940 ± 20) was back-calculated from the total mass, while MALDI-MS verified the sample purity (Fig. 5b).⁹⁵ Kumara et al. reported the synthesis and characterisation of ∼300 kDa and ∼400 kDa Au-hexanethiolate nanoparticles with compositions of approximately Au₁₃₈₅(SR)₂₄₀ and Au₂₀₀₀(SR)₂₉₀, respectively. MALDI-MS enabled compositional assignment, revealing peaks at 288 kDa and 394 kDa.⁹⁶ Vergara et al. characterised Au_∼2000(SC₆H₁₃)_∼290 nanoparticles using MALDI-MS, which detected molecular ions at ∼394 kDa (1+) and ∼200 kDa (2+), confirming a gold core of approximately 2000 atoms and ∼290 ligands (Fig. 5c). These studies showed the development in the synthesis and mass spectrometric characterisation of gold nanocrystals from ∼500 to ∼2000 atoms, demonstrating how ESI-MS and MALDI-MS serve as complementary, high-precision techniques for atomic-level compositional analysis and structural elucidation across progressively larger nanocrystal sizes.⁹⁷ Mass spectrometry provided insights into the formation, composition, and stability of silver clusters protected by 4-(tert-butyl) benzyl mercaptan (BBSH). Positive-ion ESI-MS tracked the evolution of the cluster over time, initially showing broad peaks (∼10–15 kDa), which shifted to defined clusters at 43.5 kDa after 3 h, and finally to stable 51.8 kDa clusters by 24 h, with no signs of etching (Fig. 5d). LDI-MS revealed that the 51.8 kDa cluster lost ∼18 kDa upon laser-induced cleavage of C–S bonds, corresponding to the loss of approximately 120 BBS ligands, leading to an estimated formula of Ag₂₈₀(BBS)₁₂₀. Similarly, the 43.5 kDa intermediate was assigned as Ag₂₂₃(BBS)₁₀₈.⁹⁸

Fig. 5 (a) MALDI (red) and ESI (blue) mass spectra of Au_∼500±10(SCH₂CH₂Ph)_∼120±3. MALDI-MS shows 1+ and 2+ ions, while ESI MS yields 3−, 4−, 5−, and 6− ions. (b) MALDI (red) and ESI (blue) mass spectra of Au_940±20(SR)_160±4. (c) MALDI-MS and UV–visible spectrum (inset) of Au_∼2000(SR)_∼290. (d) Positive-ion ESI mass spectra and GPC chromatograms of Ag_∼280(SBB)_∼120. Adapted from (a) ref. 94, (b) ref. 95, (c) ref. 97 and (d) ref. 98. Copyright 2014, the American Chemical Society. Copyright 2014, the American Chemical Society. Copyright 2018, the American Chemical Society. Copyright 2011, The Royal Society of Chemistry.

2.4. Nanocluster chemistry unveiled: inter-cluster reactions

Inter-cluster reactions involve the exchange of metal atoms and/or ligands between two atomically precise clusters, leading to the formation of alloy clusters, mixed ligand clusters, cluster polymers and new clusters. These reactions occur spontaneously under ambient conditions, revealing that nanoclusters are dynamic, chemically active entities.⁹⁹ These reactions were first demonstrated by Krishnadas et al. using ESI-MS to observe the real-time metal (Au–Ag) and ligand (PET–FTP) exchange between [Au₂₅(SR)₁₈] and [Ag₄₄(SR)₃₀] clusters, revealing the formation of alloys with mass shifts of 89 and 99 Da.¹⁰⁰ Building on this, Pradeep and coworkers showed that mixing of [Ag₂₅(SR)₁₈] and [Au₂₅(SR)₁₈] leads to the formation of bimetallic nanoclusters, with ESI-MS capturing a short-lived dimer intermediate, [Ag₂₅Au₂₅(SR)₅₃₆]²⁻, which enabled atomic exchange (Fig. 6a).¹⁰¹ Subsequently, Neumaier et al. developed a kinetic model based on the reaction between [Ag₂₅(DMBT)₁₈] and [Au₂₅(PET)₁₈], showing that inter-cluster exchange occurs through three steps, as follows: (i) formation of a dimer, (ii) internal exchange of metal atoms, and (iii) breakdown into alloyed monomers.¹⁰² Recently, Sooraj et al. showed that solid-state grinding of [Au₂₅(PET)₁₈] with [Ag₂₅(DMBT)₁₈] led to the rapid formation of polymer species, including dimers, trimers, and higher oligomers (Fig. 6b).

Fig. 6 (a) ESI-MS of the mixture of Ag₂₅(DMBT)₁₈(I) and Au₂₅(PET)₁₈(II), showing a feature due to the dianionic adduct, (Ag₂₅Au₂₅(DMBT)₁₈(PET)₁₈)²⁻ formed between I and II. (b) ESI-MS of Ag₂₅(SR)₁₈ and Au₂₅(SR)₁₈, and the time-dependent MS of the of Ag₂₅(SR)₁₈ : Au₂₅(SR)₁₈ (ratio 1 : 1) produced monomers, dimers, and tetramers of the exchanged species. (c) Time-dependent ESI-MS results of the conversion from ¹⁰⁹Ag₄₄(SR)₃₀ to ¹⁰⁷Ag₄₄(SR)₃₀. (d) Time-dependent ESI-MS results of the conversion from ¹⁰⁷Ag₄₄(SR)₃₀ to ¹⁰⁹Ag₄₄(SR)₃₀. Reproduced with permission from (a) ref. 101, (b) ref. 103, (c) ref. 105 and (d) ref. 105. Copyright 2016, Springer Nature Group. Copyright 2024 and 2021, the American Chemical Society.

The rate of reaction appeared to be faster in the solid state compared to the solution phase. Control experiments showed that metal exchange between clusters is the driving factor for polymerisation. The polymer species were stabilised by weak interactions such as van der Waals forces, aurophilicity, C–H⋯π and π–π stacking.¹⁰³ Isotopic labelling studies using [¹⁰⁷Ag₂₅(DMBT)₁₈]⁻ and [¹⁰⁹Ag₂₅(DMBT)₁₈]⁻ showed that all 25 silver atoms could be exchanged within a minute.¹⁰⁴ Tang et al. showed that more rigid clusters such as Ag₂₉(BDT)₁₂(TPP)₄ exchanged atoms much more slowly, proving that flexibility plays a key role in reactivity. Their study showed that all the silver atoms in Ag₄₄(SR)₃₀ can dynamically exchange with Ag(I)-thiolate via an entropy-driven, isotopic metal exchange process, occurring first in the shell, and then in the kernel. Time-dependent ESI-MS showed complete, reversible conversion between ¹⁰⁷Ag and ¹⁰⁹Ag clusters over time (Fig. 6c and d), respectively.¹⁰⁵ In a related study, Suyama et al. found that spontaneous electron transfer (not atom exchange) occurred between two PtAu₂₄ clusters, protected with different alkanethiol ligands. The longer alkyl chains stabilised the dimer intermediates, which facilitated electron transfer between the clusters. These dimers were directly observed by ESI-MS, and their stability was found to increase with an increase in alkyl chain length.¹⁰⁶

In a recent study by Acharya et al., they reported that very stable dimers were formed between [Ag₂₉(BDT)₁₂]³⁻ and [Mag₂₄(DMBT)₁₈]⁻ (M = Ag, Au, Pd, or Pt), which remained intact for up to 48 h in solution due to the strong Ag–S bonds and non-covalent interactions at the interface. Altogether, these studies prove that nanoclusters are not fixed structures but can dynamically transform through inter-cluster interactions. ESI-MS plays a central role in understanding the products and intermediates, monitoring the real-time kinetics, and elucidating the mechanism of inter-cluster reactions.¹⁰⁷

3. Mass spectrometry and structure

Ion mobility spectrometry (IM-MS) and tandem mass spectrometry (MS/MS) techniques such as collision-induced dissociation (CID), surface-induced dissociation (SID), and ultraviolet photodissociation (UVPD) are powerful approaches for probing the structure and fragmentation of metal nanoclusters. CID and SID induce fragmentation through energetic collisions, while UVPD uses light to activate ions, each revealing distinct dissociation pathways. IMS adds an additional dimension by separating ions based on their shape and size, enabling detailed insight into nanocluster conformations and fragmentation dynamics in the gas phase.

3.1. Unravelling the dissociation pathways of APCs in the gas phase

Collision-induced dissociation is a widely used MS/MS technique that enables the detailed study of the structure and stability of gas-phase ions by inducing fragmentation through collisions with inert gases such as helium, nitrogen, and argon. By accelerating mass-selected ions and causing them to collide with neutral gas molecules, CID converts kinetic energy into internal energy, leading to controlled bond cleavage within the ion. Fields-Zinna et al. applied CID MS/MS to a thiolate-protected gold nanocluster, Na_xAu₂₅(SC₂H₄Ph)_18−y(S(C₂H₄O)₅CH₃)_y, revealing that fragmentation predominantly involves the loss of the Au₂L₃ semi-ring motifs that bridge the Au₁₃ core. The major fragment ions detected include [Na₂AuL₂]⁺, [Na₂Au₂L₃]⁺, [NaAu₃L₃]⁺, and [NaAu₄L₄]⁺, with no intermediates containing Au₅–Au₁₇, indicating that the Au₁₃ core remained intact under the CID conditions.¹⁰⁸ Dass and coworkers reported the first complete structural and fragmentation analysis of an Au₂₅(SR)₁₈ nanocluster using IM-MS and CID MS/MS. This study revealed that the major fragments of Au₂₅(SR)₁₈^∓ were Au₂₁(SR)₁₄^∓ and Au₁₇(SR)₁₀^∓ formed due to the successive loss of neutral Au₄(SR)₄ fragments.¹⁰⁹ Black et al. utilised in-source CID MS to analyse larger gold NCs such as Au₁₄₄(SR)₆₀ and Au₁₃₀(SR)₅₀, observing that triply charged (3+) ions undergo more efficient fragmentation (∼80%) due to coulombic repulsion and higher energy absorption. Their fragmentation patterns involve characteristic neutral loss of disulfide ligands (SR)₂ and hydrocarbon units, with core-specific gold-containing fragments such as Au₄(SR)₄ for Au₁₄₄ and Au₃(SR)₂ for Au₁₃₀, reflecting the differences in cluster core dissociation.¹¹⁰ Chakraborty et al. demonstrated that [Ag₂₉(S₂R)₁₂]³⁻, [Ag₂₅(SR)₁₈]⁻, and [Ag₄₄(SR)₃₀]⁴⁻ exhibit distinct dissociation pathways and gas-phase stabilities, which are correlated with their geometric and electronic structures. [Ag₂₉(S₂R)₁₂]³⁻ undergoes stepwise cleavage into [Ag₂₄(S₂R)₉]²⁻ and [Ag₅(S₂R)₃]⁻, while [Ag₄₄(SR)₃₀]⁴⁻ fragments into [Ag(SR)₂]⁻ and [Ag₂(SR)₃]⁻, retaining their closed-shell configurations. [Ag₂₅(SR)₁₈]⁻ differs from its gold analogue by losing neutral Ag₃(SR)₃ units. This study found that the gas-phase stability trends (Ag₂₉ > Ag₂₅ > Ag₄₄) are correlated with the solution-phase behaviour.¹¹¹ Yao et al. revealed the atomic-level mechanism of isoelectronic size conversion from [Au₂₃(SR)₁₆] to [Au₂₅(SR)₁₈] via a surface-motif-exchange (SME)-induced core transformation from cuboctahedral to icosahedral Au₁₃. The isoelectronic size-conversion of Au₂₃ nanoclusters proceeds according to the following definitive reaction: [Au₂₃(SR)₁₆]⁻ + 2[Au₂(SR′)₃]⁻ → [Au₂₅(SR)₁₂(SR′)₆]⁻ + 2[Au(SR)₂]⁻. ESI-MS was central in tracking the real-time reaction kinetics, showing a simultaneous decrease in [Au₂₃(SR)₁₆]⁻ and increase in [Au₂₅(SR)₁₈]⁻ peak intensities, as shown in Fig. 7a. The MS/MS spectra of [Au₂₃(SR)₁₆]⁻ (Fig. 7b) undergoes sequential loss of [Au(SR)₂]⁻, [Au₂(SR)]⁻ and [Au₂₅(SR)₁₈]⁻ (Fig. 7c) and shows the dominant dissociation of [Au₂(SR)]⁻, with an increase in the collision energy. The fragmentation pathways of [Au₂₃(SR)₁₆]⁻ and [Au₂₅(SR)₁₈]⁻ are shown in Fig. 7d and e, respectively. Based on the definitive equation and according to MS/MS analysis, they constructed an SME-induced symmetry-breaking core structure transformation mechanism for the isoelectronic size-conversion reaction.¹¹² Xie and coworkers studied the molecular-level oxidative etching mechanism of water-soluble [Au₂₅(SR)₁₈] nanoclusters using time-dependent ESI-MS and MS/MS. They identified over 20 intermediate species and revealed a two-stage process, as follows: (i) rapid decomposition into smaller clusters and Au(I)-SR complexes; (ii) followed by isoelectronic recombination into larger clusters (e.g., [Au₂₄SR₂₀]⁰) or ligand-rich clusters. MS/MS revealed size-dependent fragmentation patterns and verified the evolution of the surface motifs from [Au₄SR₄] in [Au₁₈SR₁₄]⁰ to [Au₆SR₆] in [Au₂₄SR₂₀]⁰. MS/MS also revealed that larger clusters fragmented more extensively at the same collision energy, with the onset fragmentation energies generally decreasing with size, except for [Au₂₄SR₂₀]⁰.¹¹³ Surface-induced dissociation (SID) is a powerful ion activation technique, wherein mass-selected ions collide with functionalized surfaces (e.g., alkanethiol-protected gold), enabling precise probing of the fragmentation energetics and kinetics. Unlike CID, SID offers finer control over the collision energy, allowing quantitative determination of the threshold dissociation energies, activation entropies, and microcanonical rate constants. Johnson et al. used SID to demonstrate that the [Au₈(TPP)₆]²⁺ cluster exhibits greater stability toward dissociation compared to [Au₇(TPP)₆]²⁺, [Au₈(TPP)₇]²⁺, and [Au₉(TPP)₇]²⁺.¹¹⁴ Further, Baksi et al. studied Ag₁₁(SG)₇⁻ and showed that SID induced greater fragmentation and charge stripping compared to CID.¹¹⁵ MS/MS investigations have proven indispensable for understanding the fragmentation pathways, core–ligand interactions, structural integrity, and dynamic transformations in APCs. These mass spectrometric studies complement crystallographic and spectroscopic techniques by providing molecular-level insights.

Fig. 7 (a) ESI-MS of the isoelectronic size conversion from [Au₂₃(SR)₁₆]⁻ to [Au₂₅(SR)₁₈]⁻ in water. Structural relation between Au₂₃ and Au₂₅ nanoclusters. (b, c) Tandem mass spectra and (d, e) fragmentation pathways of [Au₂₃(SR)₁₆]⁻ and [Au₂₅(SR)₁₈]⁻. Adapted from (a)–(e) ref. 112. Copyright 2018, Springer Nature Group.

3.2. UVPD

Ultraviolet photodissociation (UVPD) mass spectrometry uses high-energy UV photons, typically from a pulsed laser at 193 nm (also 213 or 266 nm are used), to excite ions to electronically excited states, inducing extensive and specific fragmentation. This technique provides deeper structural insights than conventional methods such as collision-induced dissociation (CID) or electron-based methods such as electron capture dissociation (ECD) and electron transfer dissociation (ETD).¹¹⁶ Its applications extend across proteomics, including peptide sequencing and PTM localisation, top-down protein analysis, native mass spectrometry of protein complexes, as well as lipidomics, nucleic acid characterisation, and glycomics. In APCs, CID and SID produce limited fragments, whereas UVPD generates extensive, detailed fragmentation, enabling deeper structural analysis.

Black et al. performed the structural analysis of Au₂₅(pMBA)₁₈ and Au₃₆(pMBA)₂₄ clusters using UVPD, which enabled the systematic cleavage of ligand staples (Au–S and C–S bonds) without disrupting the gold core. At higher laser doses, UVPD triggered monomer evaporation, generating Au₄–Au₂₀ bare gold cluster ions from Au₂₅(pMBA)₁₈, thereby permitting the accurate determination of the ligand and gold atom counts.¹¹⁷ Li and coworkers utilised UVPD to study the size dependence of gold clusters in catalytic applications. The Au₁₄₄(PET)₆₀ cluster was fragmented by UVPD at 193 nm to generate size-selected Au_nS_m clusters (n = 12–122), and their acetylene adsorption was monitored by ESI-MS, revealing a clear size-dependent hierarchy in C₂H₂ binding. Further, they extended this study to a smaller Au₂₅ cluster and showed that acetylene binding occurs up to ∼11 molecules per cluster. These studies demonstrate that smaller clusters have significantly stronger acetylene adsorption, highlighting the distinct electronic effects that govern catalytic activity in acetylene hydrochlorination.^118,119 Jose et al. showed that UV photoactivation resulted in unique dissociation pathways in APCs such as [Ag₂₉(BDT)₁₂]³⁻ and [PtAg₂₄(DMBT)₁₈]²⁻, primarily via electron photodetachment. UVPD leads to single ligand losses, perturbing the metal–ligand interface, with dissociation characteristics different from that in collision-based methods.¹²⁰ The study by Li and coworkers provided direct experimental evidence for the photon energy-dependent photoreaction pathways of an [Au₂₅(PPh₃)₁₀(SC₂H₄Ph)₅Cl₂]²⁺ (Au₂₅) cluster and correlated these pathways with its photocatalytic performance on TiO₂ (P25). Using photodissociation mass spectrometry (PD-MS), it was found that visible light (455 nm) induces the selective loss of the PPh₃ and PPh₃AuCl ligands, while preserving the Au₂₅ core (Fig. 8a–c), exposing the active sites and enabling high catalytic activity. In contrast, UV light (193 nm) causes complete decomposition into small [Au_nS_m]⁺ fragments, leading to a reduced performance due to cluster destabilisation. Fig. 8d and e show the mass spectrum of Au₂₅ under ultraviolet light (193 nm).¹²¹ Collectively, these studies establish UVPD as a powerful technique for understanding complex nanostructures and linking their fragmentation behaviour to functional and catalytic properties with high specificity and precision.

Fig. 8 Photodissociation of Au₂₅ at 455 nm. (a) Wide-range photodissociation MS (in positive mode). (b) and (c) Enlarged views of panel a and assignment of the photofragments, respectively. (d) Wide-range photodissociation MS (in positive mode) spectrum of Au₂₅ at 193 nm. (e) Extracted region of the Au₁₉S_m (m = 0–4) species. Adapted from (a)–(e) ref. 121. Copyright 2023, the American Chemical Society.

3.3. Ion mobility–mass spectrometry (IM-MS)

Ion mobility–mass spectrometry (IM–MS) is a powerful analytical technique that separates gas-phase ions based on their size, shape, and charge by measuring their drift through a buffer gas under an electric field.^122,123 Since its early development in the 1960s and integration with ESI and MALDI,¹²⁴ IM–MS has evolved through innovations such as drift tube ion mobility spectrometry (DTIMS), travelling wave ion mobility spectrometry (TWIMS), and trapped ion mobility spectrometry (TIMS), a key tool for resolving isomers and probing gas-phase structures in fields such as structural biology, nanochemistry, and materials science. DTIMS is the most common method for the structural analysis of nanoclusters, where ions drift through a uniform electric field against a counter-flowing buffer gas. It enables direct, calibration-free calculation of collision cross sections (CCS) using the Mason–Schamp equation, making it ideal for early structural characterisation and a reference for other IMS techniques. The Mason–Schamp equation states that the mobility of an ion (K) is inversely proportional to its collision cross section (Ω), meaning that smaller, more compact ions move faster under an electric field than larger or more extended ions. Mathematically, it is expressed as follows:
where Z is the charge of the ion, e is the elementary charge, N is the number of gas molecules, μ is the reduced mass of the ion–gas pair, k_B is the Boltzmann constant, T is the gas temperature, and Ω is the ion–neutral collision cross section.¹²⁵ TWIMS uses a stacked ring ion guide with RF and transient DC voltages to generate travelling waves that propel ions through a buffer gas, separating them by mobility. Higher-mobility ions are carried by the wave, whereas lower-mobility ions roll over it, taking longer to traverse the mobility cell. Although direct CCS calculation is not possible due to the dynamic field, CCS can be determined after calibration using standards with known values.¹²⁶ TIMS is a recent innovation that traps ions by counterbalancing a buffer gas flow with a spatially varying electric field, holding them at defined positions based on their mobility, and sequentially releasing them as the electric field is reduced. This design offers high sensitivity, resolution, and improved duty cycle through synchronised accumulation and analysis. TIMS requires calibration of CCS and is widely used in structural biology and multi-omics.^127,128 The structural information obtained from ion mobility spectrometry arises from the experimentally determined CCS, which reflects the average area of an ion as it collides with the buffer gas. Compact ions with smaller surface areas exhibit lower CCS values and move faster, whereas extended structures show larger CCS values and drift more slowly. The reduced mass term in the Mason–Schamp equation accounts only for the momentum exchange between the ion and gas molecules and does not contain any structural information. Thus, the shape or conformation is inferred indirectly from the CCS, which represents the dynamic interaction of the molecule with its environment rather than its exact atomic arrangement. When the measured CCS values are combined with molecular modelling or dynamic simulations, one can identify the most probable conformation and estimate the overall structural form. Modern ion mobility instruments employing drift-tube, trapped, and travelling-wave systems routinely achieve resolving powers of 200–400, while the extended-path or cyclic systems can reach up to about 700 after nearly 100 passes. These advances allow the separation of closely related conformers and intermediate states in proteins, peptides, and nanoclusters. However, current IM–MS methods provide qualitative information on molecular compactness and topology, and accurate atomic-scale structure determination still requires complementary spectroscopic or computational validation.^129,130

IM-MS has emerged as a powerful hyphenated technique for understanding the structural complexity of atomically precise metal nanoclusters in the gas phase. In silver nanoclusters, IM-MS gave insights into gas-phase isomers, which are inaccessible through conventional mass spectrometry or crystallography. These isomers, although identical in mass, exhibited distinct drift times and CCS values, indicating significant differences in their three-dimensional structures. Baksi et al. reported the first experimental evidence for gas-phase dimers, trimers, and tetramers of Au₂₅(PET)₁₈ clusters using IM-MS, with their distinct drift times and CCS values confirming their existence. The monomer appeared at 12.7 ms (CCS = 297.8 Ų), the dimer at 10.8 ms (CCS = 453.4 Ų), and the trimer at 8.3 ms (CCS = 668.3 Ų), indicating an increase in their size and structural complexity. The formation of these aggregates was shown to be highly sensitive to the experimental conditions; increasing the He gas flow and lowering the cone voltage promoted their aggregation, while higher voltages led to their dissociation, reflecting the fragile, non-covalent nature of these gas-phase polymers.¹³¹ Pradeep and coworkers used IM-MS to demonstrate the presence of gas-phase isomers, with Ag₄₄(SR)₃₀ exhibiting multiple isomers in its 3⁻ and 4⁻ charge states, while Ag₂₉(BDT)₁₂ showed two isomers in its common 3⁻ charge state. Density functional theory calculations indicated that this isomerism originates from the variations in ligand orientations and staple rearrangements, leading to differences in the overall geometry. In contrast, no isomeric species were observed for Au₂₅(SR)₁₈ or Ag₂₅(SR)₁₈, underscoring the role of ligand chemistry and charge state in governing structural diversity.⁴⁰ Kalenius et al. provided the first experimental evidence for a gas-phase topological isomer of the well-studied Au₂₅(SR)₁₈ cluster in both anionic and cationic forms. This isomer, energetically close and topologically connected to the known ground-state structure, arises via a collective rotation of the icosahedral Au₁₃ core without breaking any Au–S bonds. The measured collision cross sections closely match theoretical predictions, and the relative abundance of the isomeric structures can be controlled by in-source activation, demonstrating that interconversion between isomers is feasible in the gas phase.¹³² Zeng et al. demonstrated how ligand exchange can influence the structural and optical properties of atomically precise silver. Partially replacing the 1,3-benzene-dithiol (BDT) ligands with dihydrolipoic acid (DHLA) in Ag₂₉(BDT)₁₂ led to a 44-fold increase in its photoluminescence quantum yield. High-resolution electrospray ionisation mass spectrometry (HRESI-MS) confirmed the successful ligand exchange (Fig. 9a), with species containing up to six substituted ligands [Ag₂₉(BDT)_12−x(DHLA)_x]³⁻ (x = 0–6). The CCS value increased from 480 to 583 Ų for x = 0–6 DHLA substitutions (Fig. 9b), which was consistent with DFT predictions and correlated with the increase in rigidity and reduced nonradiative decay.¹³³ Chakraborty et al. used trapped ion mobility spectrometry (TIMS-MS) together with density functional theory (DFT) to investigate the fragmentation dynamics of [Ag₂₉L₁₂]³⁻ clusters. This study showed that the cluster mainly dissociates by gradually losing [Ag₅L₃]⁻ units, which leads to fragments such as [Ag₂₄L₉]²⁻ and [Ag₁₉L₆]⁻. The experimental collision cross sections showed excellent agreement with DFT predictions, enabling the reliable structural assignment of these fragments. The larger [Ag₂₄L₉]²⁻ and [Ag₁₉L₆]⁻ fragments retain compact superatom-like core-staple structures, indicating that kinetic control governs dissociation rather than thermodynamic stability.¹³⁴ In another example of structural transformation, Baski et al. used TIMS to investigate alloy formation in Ag₂₉(BDT)₁₂(PPh₃)₄ nanoclusters through intercluster reactions with Cu₁₂S₆(DPPPT)₄. This study showed that up to 14 Ag atoms could be replaced by Cu atoms, corresponding to nearly 50% exchange, without disrupting the overall cluster structure. TIMS measurements revealed a linear decrease in the collision cross section (CCS) with an increase in Ag/Cu exchange (Fig. 9c), indicating a gradual size contraction. DFT-based CCS simulations confirmed that the exchanged atoms are predominantly confined to the cluster surface, while the core remains intact.¹³⁵ Roy et al. examined the interaction of [Ag₂₉(L)₁₂]³⁻ nanoclusters with a secondary ligand (L′) using ion mobility mass spectrometry (IM-MS) supported by spectroscopy and DFT. IM-MS confirmed the formation of [Ag₂₉(L)₁₂]L′_n³⁻ adducts (n = 1–4), with distinct mass separations (∼m/z 116 per ligand). A systematic increase in collision cross-sections (CCSs) was observed as more L′ ligands attached, directly evidencing the progressive structural expansion of the nanocluster. The IM-MS data correlated closely with DFT models, validating the structural assignments. Fig. 9d clearly shows this trend, with mobilograms shifting to higher CCS values for each additional ligand, highlighting the sequential and specific nature of L′ binding.¹³⁶ These studies highlight the role of IM-MS in revealing the dynamic, structural behaviour of ligand-protected metal nanoclusters, establishing it as an essential tool for probing isomerism, aggregation, ligand interactions, and compositional tuning at the atomic scale.

Fig. 9 (a) ESI MS of an Ag₂₉(BDT)_12−x(DHLA)_x NC solution showing a maximum of six ligands exchanged. An expanded view (black trace) is presented in the inset with the corresponding calculated spectra (red trace). A further expanded view of the MS spectrum of Ag₂₉(BDT)_12−x(DHLA)_x³⁻ with x = 1, which resolves the isotopologue distribution and shows an exact match with the calculated spectrum. (b) Drift time profile of Ag₂₉(BDT)_12−x(DHLA)_x³⁻ measured in IM mode, showing an increase in the size of the ligand exchanged NCs. (c) Extracted ion mobilograms, that is, ion intensity versus CCS, determined for Cu_xAg_29−x(BDT)₁₂³⁻ (x = 0–14) by TIMS-TOFMS. (d) Mobilograms of individual [Ag₂₉]L′_n³⁻ (n = 0–4) ions showing an increase in CCS with an increase in the number of L′-adducts to [Ag₂₉]³⁻ NCs. Reproduced with permission from (a) ref. 133, (b) ref. 133, (c) ref. 135 and (d) ref. 136. Copyright 2021, 2020 and 2025, the American Chemical Society.

The cyclic ion mobility–mass spectrometry (cIM-MS) system is a significant advancement over conventional IM-MS, built on a Waters SYNAPT G2-Si platform with a 98 cm closed-loop travelling-wave (TW) ion mobility separator. Its racetrack-like geometry allows ions to traverse the mobility cell multiple times, increasing the resolving power with the square root of the number of passes from approximately 78 in a single pass to approximately 750 after 100 passes, providing “dial-up” mobility resolution. This instrument features a flexible electrode array and software-controlled optics, enabling multifunction experiments such as mobility selection, ion storage, activation, and IMSⁿ, while maintaining high ion transmission. Fig. 10a schematically represents the instrument layout, highlighting the cIM device orthogonal to the main ion path, integration with quadrupole and TOF analysers, and associated ion guides and chambers. This design extends the IM-MS capabilities to the high-resolution, multifunctional structural analysis of molecular species.¹³⁷ Its applications include the separation of isomeric pentasaccharides¹³⁸ and conformational studies of ubiquitin ions,¹³⁹ showcasing its ability to probe complex gas-phase structures.

Fig. 10 (a) Schematic showing the Q-cIM-ToF instrument. (b) Arrival time distributions recorded after 10 separation passes using cyclic ion mobility spectrometry (cIMS): (A) (0,0), (B) (1,0), (C) (2,0), and (D) (3,0) ions. The ^TWCCS_N2 values of the isomers of these species are indicated. These are mean values based on three different measurements. The standard error of the mean is within ±0.3 Ų. (c) Plot of experimental ^TWCCS_N2 values (blue dots; lines are meant to guide the eye) obtained from (lower resolution) single pass measurements for the full range of (m,n) fragment ions as a function of their m/z values. Adapted from (a) ref. 137, (b) ref. 140 and (c) ref. 140. Copyright 2019 and 2025, the American Chemical Society, respectively.

Kappes and coworkers demonstrated the power of multi-pass cIM-MS in resolving subtle structural changes during the thermal decomposition of [Pt₁₇(CO)₁₂(PPh₃)₈]²⁺ clusters. Gas-phase CID coupled with cIM-MS resolved distinct isomeric fragments after CO desorption, with CCS differences of less than 1%, indicating CO loss from nonequivalent sites. Fig. 10b shows that sequential CO loss from [Pt₁₇(CO)₁₂(PPh₃)₈]²⁺ produces multiple structural isomers, as revealed by the distinct ion mobility peaks. (0,0) shows that the intact parent ion [Pt₁₇(CO)₁₂(PPh₃)₈]²⁺ has a single, well-defined structure with no isomeric forms. Upon sequential CO loss ((1,0) to (3,0)), the ion mobility spectra reveal multiple peaks, indicating the emergence of different isomeric structures. Fig. 10c presents the overall trend in CCS versus m/z for the fragment ions, showing an initial linear decrease in size as CO and benzene are lost, followed by a steeper decline when higher-energy pathways, such as phenyl and H₂ elimination, generate a more compact and reorganised cluster framework. DFT calculations validated the observed fragment geometries. The Pt₁₇ core remains robust throughout, demonstrating its stability.¹⁴⁰

Similarly, Hennrich et al. used cIM-MS to study the superatom dianions [Mau₂₄(C≡CR)₁₈]²⁻ (M = Ni, Pd, and Pt), achieving the precise separation of three structurally analogous clusters based on minor CCS variations (Ni: 721.5 Ų, Pd: 723.3 Ų, and Pt: 724.9 Ų) after 50 passes. The high resolving power enabled direct correlation with both the crystallographic data and DFT models, confirming that the gas-phase geometries closely mirrored their solid-state analogues. Interestingly, the Ni-centred cluster exhibited energy-dependent isomerisation under collision-induced activation, producing a larger, previously unobserved structural form, while its Pd and Pt analogues remained conformationally stable. This demonstrates the ability of cIM-MS not only to resolve minute structural differences but also to capture dynamic isomerisation phenomena.¹⁴¹

cIM-MS opens new avenues for exploring the structural and dynamic behaviour of metal nanoclusters and complex molecular assemblies. Future research can utilize its ultra-high resolution and multi-pass capabilities to resolve subtle isomeric differences, monitor real-time conformational changes, and map detailed fragmentation pathways.

4. Expanding properties

The electronic properties of APCs are often studied in solution; however, solvent and counterion effects can distort the results. Thus, to overcome these limitations and understand the exact electronic structure, gas-phase techniques such as anion photoelectron spectroscopy (PES) are employed. PES directly measures fundamental parameters such as the HOMO–LUMO gap and electron affinity of mass-selected cluster anions in a vacuum, eliminating solvation and ion-pairing effects.¹⁴² Mass selection is a critical component of PES measurements, given that it isolates specific cluster ions and prevents spectral overlap or interference. Enhancements such as increased ion beam intensity and reduced laser fluence improve the measurement precision by minimising multiphoton artefacts. This allows the accurate determination of the electron binding energies, detachment dynamics, and superatomic orbital structures, revealing the core electronic features of nanoclusters. Multiple studies demonstrated the strength of mass-selected PES in uncovering the intrinsic behaviour of nanoclusters. Hirata et al. reported the first PES of [Au₂₅(SC₁₂H₂₅)₁₈]⁻, confirming its superatomic (1S)²(1P)⁶ electronic configuration and revealing an adiabatic electron affinity (AEA) of 2.2 eV, which is significantly lower than theoretical predictions. This highlighted the discrepancies between theory and experiment in modelling these clusters.¹⁴³ Similarly, Hamouda et al. investigated [Au₂₅(SG)₁₈ − 6H]⁷⁻, a highly charged glutathione-protected cluster, and showed that its gas-phase optical absorption closely matches its solution-phase spectrum. This indicated that the core electronic structure remains stable across environments, with photodetachment occurring via tunnelling through a Coulomb barrier rather than fragmentation.¹⁴⁴ Tasaka et al. studied a silver cluster [Ag₄₄(SC₆H₃F₂)₃₀]⁴⁻ and inferred that the cluster possesses unique stability despite its negative electron affinity. Electron loss was suppressed due to its strong repulsive Coulomb barrier, and fragmentation occurred preferentially through ligand–metal bond dissociation. PES, coupled with DFT and tunnelling models, elucidated the detachment mechanism and confirmed an 18-electron superatom structure.¹⁴⁵ Ito et al. made some refinements in the PES measurements and studied ligand-protected M₁₃ clusters. They identified that the previously known electron affinity values of M₁₃ clusters were underestimated due to multiphoton effects. Owing to the improved ion intensity and reduced laser fluence, they measured more accurate AEA values, validating the theoretical models.¹⁴⁶

Doping and ligand modifications were shown to modulate the electron affinities without altering the overall superatomic electronic framework. Kim et al. studied the PES of doped superatoms such as [XAg₂₄(SR)₁₈]⁻ (X = Ag and Au) and [YAg₂₄(SR)₁₈]²⁻ (Y = Pd and Pt). They observed that doping with Pd and Pt significantly shifted the superatomic orbital energies and reduced AEAs, which was attributed to the changes in the core charge and Coulomb interactions. However, despite these energy shifts, the orbital ordering and HOMO–LUMO gaps remained consistent.¹⁴⁷ Further, Ito et al. tested the supervalence bond (SVB) model for bi-icosahedral gold clusters, specifically the Au₂₃ core in Au₃₈(PET)₂₄. Neutral precursors, [M₁Au₃₇(PET)₂₄]⁰ (M = Pd and Pt), which are isoelectronic and structurally similar to Au₃₈(PET)₂₄, were synthesised and chemically reduced to form [M₁Au₃₇(PET)₂₄]⁻ anions. The gas-phase anion (PES) of these mass-selected clusters revealed spectral features consistent with the superatomic orbital interactions predicted by the SVB model, providing direct experimental support for the bonding framework.⁴¹ Akazawa et al. investigated the intrinsic electronic structure of the gold nanocluster [Au₃₈(PET)₂₄]⁰ by measuring its HOMO–LUMO gap using gas-phase PES on the MALDI-generated [Au₃₈(PET)₂₄]⁻ anion. In their custom-built experimental setup (Fig. 11a), they integrated a MALDI source for ion generation, a time-of-flight mass spectrometer for mass selection, and a magnetic-bottle photoelectron spectrometer for electron kinetic energy analysis. This setup enabled stable generation and precise measurement of cluster anions in vacuum. The MALDI MS measurements confirmed the presence of an intact [Au₃₈(PET)₂₄]⁻ cluster and its fragmentation products (Fig. 11b). Fig. 11c presents the photoelectron spectra recorded at 266 nm and 213 nm, revealing the key spectral features attributed to electron detachment from the singly occupied molecular orbital (SOMO) and HOMO orbitals. Analysis of these spectra yields a direct gas-phase HOMO–LUMO gap of 0.78 ± 0.06 eV, which is smaller than the previously reported solution-phase values. This discrepancy was attributed to the structural changes upon reduction, notably the elongation of the Au₂₃ core due to the occupation of an antibonding orbital.¹⁴⁸ Recently, Tsukuda and coworkers used anion photoelectron spectroscopy and DFT to investigate how deprotonation of [Au₂₅(pMBA)_18−nH⁺]⁽ⁿ⁺¹⁾⁻ affects the electronic structure of its Au₁₃ (8e) core.¹⁴⁹

Fig. 11 (a) Schematic of the experimental apparatus. (b) Negative-mode MALDI mass spectrum of [Au₃₈(PET)₂₄]⁻. (c) PE spectra of [Au₃₈(PET)₂₄]⁻ recorded with a 266 nm laser (red) and 213 nm laser (blue). Reproduced with permission from (a)–(c) ref. 148. Copyright 2025, the American Chemical Society.

Overall, gas-phase PES, in combination with high-resolution mass spectrometry and theoretical modelling, offers a robust and solvent-free platform for investigating the fundamental electronic structure of nanoclusters. It provides precise information on the superatomic orbitals, electron detachment processes, and the effects of structural and compositional modifications, thereby broadening our understanding on the superatom behaviour of nanoclusters.

5. Additional advances

5.1. CDMS

Charge detection mass spectrometry (CDMS) is a powerful analytical technique designed to overcome the limitations of traditional MS to analyse very large and heterogeneous nanomaterials, such as megadalton-sized nanoparticles, self-assembled nanoclusters, and virus assemblies. Conventional MS struggles to characterise these samples due to the overlapping charge states, broad mass distributions, and extremely high mass-to-charge (m/z) ratios, which reduce the detection efficiency and resolution.¹⁵⁰

CDMS directly measures both the charge (z) and m/z of individual ions independently, enabling precise mass determination without assumptions about charge states. The instrument detects the image charge induced when ions pass through a conductive cylinder, combined with ion velocity and energy measurements, to calculate absolute mass. Since the initial coupling of CDMS with electrospray ionisation by Fuerstenau and Benner in 1995, CDMS has evolved significantly, especially through advances such as electrostatic linear ion traps (ELIT), which allow repeated single-ion measurements and improved charge resolution.

This technique excels at characterising large, heterogeneous biological assemblies, nanoparticles, and polymer assemblies, providing insights into their mass distribution spanning from the megadalton to gigadalton range. For example, studies on ligand-protected gold nanoclusters and their zinc-induced aggregates revealed broad mass distributions (∼75 MDa to >1 GDa), highlighting the ability of CDMS to analyse complex hierarchical nanomaterials with sub-30 nm dimensions. CDMS has also been successfully applied to synthetic polymer nanoobjects. Doussineau et al. developed a setup combining two charge detection devices (CDDs) with infrared multiphoton dissociation (IRMPD) to perform MS/MS on single megadalton ions, such as 7 MDa polyethylene oxide and 31.5 MDa lambda phage DNA. This single-ion MS/MS approach enabled ion trapping and repeated irradiation, allowing detailed, ensemble-free analysis of fragmentation dynamics in large molecules.¹⁵¹ Charleux and coworkers reported the first direct molar mass and mass distribution measurements of self-assembled amphiphilic block copolymer nano-objects without model-based assumptions, revealing their narrow mass distributions and charges approaching Rayleigh limits.¹⁵² Advancements in instrumentation have further expanded the capabilities of CDMS. William's group developed the single particle analyser of mass and mobility (SPAMM), integrating CDMS with tandem MS (MSⁿ) and ion mobility measurements on individual ions up to 8 MDa. SPAMM tracks the ion kinetic energy, fragmentation through multiple stages, and ion mobility differences, revealing the dynamic behaviour, structural heterogeneity, and fragmentation pathways in large polymer ions. This represents a major leap in analysing large, complex ions with integrated mass, charge, and mobility data.¹⁵³ Elliott et al. demonstrated that CDMS can simultaneously determine the mass and collisional cross-section of multiply charged protein ions by analysing frequency shifts during ion trapping. This provides structural information, along with accurate mass measurements, which is crucial for large heterogeneous proteins that are difficult to study using conventional methods.¹⁵⁴ Todd et al. achieved a significant improvement in the resolution of CDMS through dynamic charge calibration and enhanced electrostatic linear ion trap design, attaining charge uncertainties below 0.2 elementary charges and m/z resolving power near 330. This enabled the resolution of highly heterogeneous viral assemblies and the tracking of intermediate species with unprecedented precision, which solidifies CDMS as a powerful tool to analyse complex biomolecular systems.¹⁵⁵

Harper et al. demonstrated that CDMS can rapidly measure the mass and charge of thousands of individual ∼100 nm nanoparticles with sub-nanometer diameter resolution and about 1% mass uncertainty. Unlike TEM, CDMS offers faster analysis, high throughput, and sensitivity to surface chemistry, distinguishing nanoparticle populations based on charge differences even when their masses are similar. This positions CDMS as a powerful complementary tool for nanoparticle density determination, surface analysis, and quality control.¹⁵⁶ Orbitrap-based CDMS has also advanced considerably in the past decade. The Heck group demonstrated that multi-megadalton ions remain remarkably stable in the Orbitrap analyser, surviving extended gas-phase collisions mostly via solvent loss. Using a frequency-chasing method to correct transient frequency drifts, they achieved mass resolutions up to 100 000 and sub-10 ppm accuracy for large particles such as viral capsids.^157,158

The Jarrold group demonstrated CDMS and Orbitrap-based individual ion mass spectrometry (I2MS) as breakthrough techniques for analysing large, heterogeneous biomolecules such as viruses, gene therapy vectors, and vaccines. CDMS uses an electrostatic linear ion trap (ELIT) for repeated ion detection, achieving sub-charge-unit resolution and high throughput (>100 ions per s).¹⁵⁹ Sooraj et al. investigated the charging behaviour of ligand-protected gold nanoparticles using CDMS coupled with ESI. They compared the charging behaviour of 20 nm Au-MUTAB (50 MDa) and 60 nm Au-citrate NPs (1.3 GDa). The results showed that Au-MUTAB achieved a charging state higher than the Rayleigh limit for a 20 nm water droplet (z/z_R ≈ 2.1) (Fig. 12a). However, Au-citrate NPs could achieve only a charging of ∼0.45 times the Rayleigh limit, under identical conditions (Fig. 12b). This study correlated charging capacity under ESI with the ligand–gold binding energy, estimating 1.05 eV for Au-MUTAB and 0.09 eV for Au-citrate. This work demonstrated the ability of CDMS to quantitatively probe the ligand binding strength and confirmed its utility in analysing large nanoparticles with complex interfaces and high heterogeneity.¹⁶⁰

Fig. 12 (a) Charge vs. size plot of Au-MUTAB nanoparticles. (b) Charge vs. size plot of Au–citrate nanoparticles. Adapted from ref. 160. Copyright 2025, the American Chemical Society.

Charge detection mass spectrometry (CDMS) has achieved significant progress in the accuracy of charge detection, advancing from early systems limited by electronic noise to modern instruments capable of unit charge resolution.^161,162 Improvements such as random trapping mode, cryogenically cooled junction field-effect transistor (JFET),¹⁶² extended trapping times, and dynamic calibration have reduced the charge uncertainty to below 0.2 e. Meanwhile, feedback-free charge-sensitive amplifiers now permit the detection of singly charged ions with high precision.¹⁶³ Orbitrap-based CDMS typically achieves a charge accuracy of 1–3e, whereas custom instruments demonstrate sub-charge resolution.^164,165 However, despite these advances, CDMS faces experimental challenges in ionizing and analysing large particles, where low ionization yields, nonvolatile buffers, and insulating ligands impede efficient charge transfer and desolvation.¹⁶⁶ Buffer exchange in volatile, ESI-compatible solvents can compromise the integrity of nanoparticles, and the single-ion detection mode inherently limits the throughput. Emerging solutions such as multiplexed detection and improved ion-optical designs aim to enhance the sensitivity and accommodate complex, heterogeneous nanosystems. With the availability of commercial CDMS instruments with high resolution, studies on NCs will reach new heights.

5.2. Mass photometry

Mass photometry (MP) is a label-free optical technique that enables the direct measurement of the molecular mass of individual particles in solution by detecting their interferometric scattering (iSCAT) signal upon landing on a surface. It relies on the proportionality between scattering contrast and molecular mass, allowing rapid and quantitative analysis under native conditions. The interferometric contrast, arising from the interference between scattered and reflected light at the glass–buffer interface, scales linearly with mass and is calibrated using known standards. Accurate conversion requires calibration in the same buffer as the sample, given that small refractive-index mismatches can introduce errors. Solvent-related interference, seen as baseline noise or contrast instability, can arise from impurities, buffer composition, temperature shifts, or surface contamination. These effects are minimized by filtering (0.22 µm) the buffer, maintaining a moderate ionic strength (≥10 mM), reducing the glycerol and detergent levels, and equilibrating the samples and optics to room temperature. Under these optimized conditions, MP provides a stable and reproducible linear relationship between scattering contrast and molecular mass, enabling precise single-particle mass measurements in complex environments.¹⁶⁷

Taylor et al. established iSCAT microscopy as a highly sensitive platform for detecting unlabeled biomolecules, smaller nanoparticles (∼2 nm), and proteins (∼50–65 kDa), with nanometer spatial and sub-millisecond temporal resolution. This study emphasised the linear response of iSCAT with particle volume and its utility in tracking viruses and proteins in real-time, without photobleaching or labelling.¹⁶⁸ Building on this, Melo et al. developed an optimised iSCAT setup with ratiometric imaging to accurately measure gold nanoparticles (<20 nm) in solution. They demonstrated the high-throughput, real-time classification of thousands of particles per minute, and revealed diffusion-limited deposition behaviour, where larger particles reached the surface earlier due to their slower diffusion. The obtained particle size distribution was in good agreement with the TEM results, validating the accuracy of this method. The application of MP has recently been extended beyond biological samples to nanoclusters.¹⁶⁹ Roy et al. extended MP to study the solvent-induced aggregation of atomically precise silver–gold alloy nanoclusters, [Ag_11−xAu_x(DPPB)₅Cl₅O₂]²⁺ (Fig. 13a). Using β-amylase and thyroglobulin standards, they calibrated MP in the range of 50–660 kDa (r² = 0.9999, ∼5% error). Fig. 13b shows the instrumental setup and mechanism of MP. In the experiment, initially, NC aggregates are dispersed in a solvent mixture and land on a non-coated glass surface. Upon landing, each particle causes a localised reduction in reflected light intensity due to interferometric scattering. These events are captured optically as dark spots, and the scattering contrast is quantitatively linked to mass using calibration curves. The schematic shows the flow from solution to detection, i.e., nanoclusters aggregate in the solvent, deposition on the glass surface, and optical detection via a high numerical aperture objective lens through immersion oil. MP revealed that the average mass increased from 65 to 103 kDa with an increase in the solvent polarity, corresponding to aggregation numbers of 13 to 50 nanoclusters (Fig. 13c). Time-resolved MP measurements captured the real-time aggregation dynamics, which correlated well with the cryo-EM and room-temperature TEM results, confirming the growth and hollow-sphere morphology of the aggregates.³³

Fig. 13 (a) (i) Calculated structure (x = 2), (ii) metal, Ag_11−xAu_xcore (x = 2), and (iii) ESI MS of [Ag_11−xAu_x(DPPB)₅Cl₅O₂]²⁺ (x = 1–5) nanoclusters. In the inset, calculated isotopic distribution is stacked with the experimental one. (b) Concept and experimental implementation of MP. Parts in the graphic representation: (1) solvent mixture (sol mix) containing nanoclusters; (2) nanocluster aggregates in solution; (3) glass surface; (4) immersion oil; and (5) objective lens. Single-particle landing event on a non-coated cover slide is shown on the right. (c) Stacked plot of the MP histogram of various-sized nanoaggregates with the counts of particle landing events and varying solvent composition. Adapted from ref. 33. Copyright 2024, The Royal Society of Chemistry.

6. Non-noble metal nanoclusters

The study of non-noble metal nanoclusters, particularly those derived from first-row transition metals such as cobalt (Co), iron (Fe), and nickel (Ni), has significantly broadened the scope of atomically precise materials beyond the traditional gold and silver systems. These clusters exhibit diverse electronic, magnetic, and catalytic properties.^170–172 MS has emerged as an indispensable technique, providing insights into their composition, stability, and growth mechanisms. The composition of the well-known cobalt sulfide superatom [Co₆S₈L₆]⁺ (L = ligand) was established through high-resolution mass spectrometric analysis. ESI-MS confirmed the precise size and monodispersity of neutral nickel nanoclusters such as Ni₄(PET)₈ and Ni₆(PET)₁₂, sometimes requiring the addition of agents such as cesium acetate (CsOAc) to facilitate ionization, yielding species such as [Ni₆(PET)₁₂ + Cs]⁺.¹⁷³ MS plays a key role in understanding the atom-by-atom substitution and redox behavior in non-noble metal nanoclusters. Gholipour-Ranjbar et al. demonstrated the incorporation of up to six Fe atoms into the cobalt sulfide core of [Co_6−xFe_xS₈L₆]⁺ clusters, whereas Ni substitution yielded only the singly substituted species [Co₅NiS₈L₆]⁺, reflecting distinct substitution energetics. MS further revealed the pronounced redox sensitivity of Fe-doped clusters, which readily oxidized in solution to generate abundant doubly charged species [Co_6−xFe_xS₈L₆]²⁺ (particularly for x ≥ 4), highlighting their higher oxidation propensity compared to their Ni- or Co-only analogues.¹⁷⁴ Beyond composition, CID studies gave important information about the bonding and gas-phase stability of these clusters. CID analysis of [Co₅MS₈L₆]⁺ clusters (M = Mn, Fe, Co, and Ni) revealed that sequential ligand loss is the dominant pathway, which competes with the unusual loss of ligand sulfide (LS). Fe-substituted clusters, such as [Co₅FeS₈L₆]⁺, demonstrated substantially reduced stability towards the first ligand loss compared to their Ni- or Co-analogs, characterised by lower collision energies needed for 50% fragmentation (CID_50%), indicating weaker metal–ligand bonds.¹⁷⁵ Li et al. utilized ESI-MS and IM–MS to elucidate the composition and structure of a nickel chalcogenide nanocluster, [Ni₃S₃H(PEt₃)₅]⁺, unlike the M₆S₈ frameworks typically formed from Co or Fe precursors. The observed m/z 863.1792 peak and isotopic pattern validated its composition (Fig. 14a), while deuteration studies showed that hydrogen is incorporated during synthesis. IM–MS analysis, supported by theoretical CCS calculations, confirmed a planar Ni₃S₃ core and the absence of isomers.¹⁷⁶ ESI-MS played a central role in confirming the composition and charge states of the open-shell nanocluster [Ni₃₀S₁₆(PEt₃)₁₁], revealing peaks corresponding to its mono- and di-cationic species at m/z 3572.43 and 1786.20, respectively. In situ ESI-MS monitoring further elucidated its formation pathway through smaller intermediates, such as [Ni₈S₅(PEt₃)₇]⁺, [Ni₂₀S₁₂(PEt₃)₇]⁺, [Ni₂₁S₁₄(PEt₃)₇]⁺, [Ni₂₁S₁₄(PEt₃)₈]⁺, [Ni₂₃S₁₄(PEt₃)₉]⁺ and [Ni₂₆S₁₄(PEt₃)₁₀]⁺, establishing the sequential cluster growth mechanism leading to the final Ni₃₀ species.¹⁷⁷ Higaki et al. recently reported a 55-atom iron cluster, which has been characterized via ESI-MS, confirming the dicationic formula [Fe₅₅H₄₆(PtBu₃)₁₂]²⁺ (Fig. 14b). Deuterium labeling coupled with ESI-MS further traced the H/D exchange pathways, revealing extensive hydrogen mobility across the cluster surface and ligand framework during synthesis, while the final species remained exchange-inactive.¹⁷⁸

Fig. 14 (a) Representative positive-mode ESI mass spectrum of cationic Pet₃-ligated nickel sulfide NCs. The inset shows the experimental isotopic pattern (blue) of [Ni₃S₃H(PEt₃)₅]⁺ overlaid with the calculated pattern (red). (b) Positive-mode ESI mass spectra of Fe₅₅ in THF. Insets show the observed and simulated isotope patterns of the major peaks. Adapted from (a) ref. 176 and (b) ref. 178. Copyright 2025, John Wiley and Sons. Copyright 2025, the American Chemical Society.

These studies highlight how advances in MS have transformed the understanding of non-noble metal nanoclusters, providing atomic-level insights into their composition, substitution behavior, structural motifs, and hydride dynamics.

7. Materials and applications of ESI

ESI-MS, traditionally an analytical technique, has undergone a significant transformation into a powerful preparative method for materials synthesis, through techniques such as electrospray deposition (ESD) and ion soft landing (SL). These approaches enable precise control over composition, morphology, thickness, and surface patterning, without the need for additives, ligands, or reducing agents.^179–181 ESD is a simple, ambient method that deposits charged microdroplets onto substrates, where solvated ions nucleate into nanostructures.¹⁸² It supports the fabrication of diverse materials, including nanoparticles,¹⁸³ nanowires,¹⁸⁴ nanosheets,¹⁸⁵ nanobrushes,¹⁸⁶ nanoclusters,¹⁸⁷ and onion-like carbons.¹⁸⁸ ESD was employed to directly deposit hierarchically structured TiO₂ spheres onto FTO substrates, serving as efficient photoelectrodes in dye-sensitised solar cells.⁴² In another example, ESD enabled the fabrication of hydrophilic–hydrophobic patterned silver nanowire “nanobrushes” that mimic natural water-harvesting systems and achieved record efficiencies in atmospheric moisture collection.⁴³ Using a home-built nano-electrospray source (Fig. 15a), Jose et al. deposited charged microdroplets of a Co₆S₈ cluster solution onto ultrapure water, forming a transparent thin film of vertically aligned nanoplates (Fig. 1b) (∼200 nm thick and ∼600 nm edge length). The nanoplates of Co₆S₈ cluster formed via electrospray deposition provide a high surface area, catalytically active film enabling the sensitive and selective electrochemical detection of As³⁺ in water.¹⁸⁹ Jana et al. fabricated a porous, luminescent Cu₄@ICBT film via ambient electrospray deposition (ESD) that selectively and reversibly senses nitroaromatic vapours.¹⁹⁰

Fig. 15 (a) Schematic of our home-built electrospray setup. The inset shows a photographic image of the nanospray plume generated from the tip of the capillary. The plume is visualized using a green laser, which scatters from it. (b) Large-area FESEM micrographs of the vertically aligned nanoplates. (c) Schematic of mass-selective cryo-EM sample preparation using the native ES-IBD workflow. Adapted from (a)–(b) ref. 189 and (c) ref. 198. Copyright 2023, the American Chemical Society. Copyright 2022, National Academy of Sciences.

SL is a mass-selective technique that deposits intact polyatomic ions onto surfaces at low kinetic energies (∼10 eV), preserving their molecular structure and charge state. It enables contamination-free fabrication due to the absence of counterions and allows precise control over surface composition and functionality.^191,192 SL has been used to prepare atomically defined metal clusters (e.g., Ni_n, Pt_n, and Au_n) for catalytic CO oxidation,¹⁹³ designing redox-active electrode–electrolyte interfaces with polyoxometalates,¹⁹⁴ and fabricating protein microarrays¹⁹⁵ with retained biological activity.¹⁹⁶ Johnson et al. demonstrate that soft landing of mass-selected ions enables the preparation of clean, high-coverage, monodisperse Au₁₁ clusters on surfaces, overcoming the limitations of solution synthesis and facilitating precise structural analysis by TEM/STEM.¹⁹⁷ A notable extension is native electrospray ion-beam deposition (native ES-IBD), which enables the solvent-free, mass-selected deposition of folded proteins for cryo-EM. A schematic representation of mass-selective cryo-EM sample preparation using the native ES-IBD workflow is shown in Fig. 15c. It avoids ice formation and contamination, yielding homogeneous, structurally intact samples suitable for 3D reconstruction, bridging mass spectrometry and structural biology.¹⁹⁸

ESD and SL extend electrospray ionisation into material synthesis by enabling the controlled deposition of ions or charged droplets onto surfaces. SL allows mass and charge-selected species to be precisely immobilised, ideal for chemically defined interfaces, while ESD enables the ambient, ligand-free fabrication of diverse nanostructures (e.g., nanoparticles, nanosheets, and nanobrushes) with tunable morphology and functionality, which are applicable in catalysis, sensing, and bioimaging.

8. MS-guided insights into catalysis

Mass spectrometry has developed rapidly in recent years and has established itself as a central technique in nanoscience for characterising materials at the atomic level. Nanocluster chemistry demands a precise understanding of the composition, structure, and electronic properties of APCs, which makes mass spectrometry a primary tool for their characterisation. In several aspects of nanoclusters, MS provides greater insights than the established methods, such as electron microscopy and optical spectroscopy. It allows high-resolution mass analysis and helps understand their growth mechanisms, reaction kinetics, fragmentation pathways, and structure–property relationships. These aspects are key to designing new functional nanomaterials. MS-based insights into cluster composition and ligand dynamics also help identify active sites and correlate structural features with catalytic, optical, and electronic behaviour, advancing the rational design of functional materials.

Recent studies show that mass spectrometry not only helps in characterising nanoclusters but also provides direct understanding of their catalytic behaviour. In situ and real-time mass spectrometric studies allow the detection of short-lived intermediates and reaction products formed during catalysis.¹⁹⁹ These observations help identify the active sites and the role of supports or ligands in promoting specific reaction steps. For example, real-time MS tracking of photocatalytic degradation on g-C₃N₄ and TiO₂ revealed their distinct oxidative pathways under visible and UV light, while Pd-based systems showed surface-specific dehydrogenation behaviour, clarifying the active roles of metal sites and supports.²⁰⁰ Similarly, deep-learning-enabled single-particle mass spectrometry now quantifies the reaction products from individual nanoparticles, linking their surface structure to catalytic turnover with unprecedented precision.²⁰¹ Together, these developments establish MS as a predictive tool for correlating atomic-scale composition and ligand dynamics with macroscopic properties such as activity, selectivity, and stability. This approach also extends to other fields such as photonics and nanoelectronics, where MS-based insights are being used to design materials with improved optical, electronic, and chemical properties.

9. Current limitations and challenges

Although mass spectrometry has emerged as a powerful technique for studying atomically precise nanoclusters, several challenges continue to restrict its wider application. The ionisation efficiency of large or weakly charged clusters remains low, leading to signal suppression and incomplete detection, while maintaining the integrity of fragile species during soft ionisation remains a persistent concern. Techniques such as ESI and MALDI, though gentle, can still induce partial fragmentation or ligand loss, complicating structural interpretation. Its quantitative accuracy is further affected by overlapping charge states, adduct formation, and matrix-dependent effects. Instrumental limitations also pose constraints; the transmission efficiency of large ions is often low, and the resolving power of most analysers decreases significantly at higher mass ranges, limiting the precise characterisation of high-nuclearity clusters and assemblies.

Ion mobility–mass spectrometry (IM–MS) provides valuable insights into molecular compactness and conformational states through the experimentally determined CCS, but it also has limitations. The CCS reflects an averaged measure of ion–gas interactions and does not directly describe atomic-level structures. Consequently, reliable interpretation requires correlation with molecular modelling or dynamics simulations. Although modern drift-tube, trapped, and travelling-wave instruments typically achieve resolving powers of 200–400, and cyclic designs may extend this to about 700, both their mass range and resolution remain insufficient for large and heterogeneous nanoclusters.

Overcoming these limitations will require improved intact ionisation methods, higher transmission efficiency, and ultrahigh-resolution instruments capable of maintaining precision at extended mass ranges. The continued integration of IM–MS with spectroscopic and theoretical approaches will be essential for achieving accurate structural determination, reliable structure–property correlations, and a predictive understanding of nanocluster behavior across different environments.

10. Conclusions and future perspectives

Recent advances in mass spectrometry have positioned it as a central analytical method in nanoscience for characterising materials at the atomic level. Nanocluster chemistry demands a precise understanding of the composition, structure, and electronic properties, which makes mass spectrometry a primary tool for the characterisation of APCs. In several aspects of nanoclusters, MS provides greater insights than the established methods, such as electron microscopy and optical spectroscopy. It allows high-resolution mass analysis and helps understand the growth mechanisms, reaction kinetics, fragmentation pathways, and structure–property relationships. These aspects are key to designing new functional nanomaterials. MS-based insights into cluster composition and ligand dynamics also help identify active sites and correlate structural features with catalytic, optical, and electronic behaviour, advancing the rational design of functional materials. A summary of APCs characterized by MS to date is provided in Table 1.

Table 1 Summary of atomically precise nanoclusters characterised by mass spectrometry thus far (as of July 31, 2025, using Web of Science using “nanoclusters”, “metal clusters”, “mass spectrometry” and “mass” as keywords). Unprotected or naked clusters are not included. The list is alphabetical and in ascending order of nuclearity of clusters. Alloy clusters, listed separately, are arranged in ascending order of total nuclearity. For each nuclearity, alphabetical order is followed

Core	Ligands	Composition	Counter ions	Ionization	Fragmentation/ion-mobility/mass selected PES	Ref.
Ag2	1,1-Bis(diphenylphosphino)methane	Ag2(dppm)2(AcO)2		ESI-MS		213
Ag6	Oligonucleotide dC12	(Ag^+)6 dC12^10−		ESI-MS		214
Ag6	Diisopropyldithiophosphate, 1,1-bis(diphenylphosphino)methane	[Ag6{S2P(O^iPr)2}4(dppm)2]		ESI-MS		215
Ag6	1,1-Bis(diphenylphosphino)methane	Ag6(dppm)4(AcO)3	OAc^−	ESI-MS		213
Ag7	2,3-Dimercaptosuccinic acid	Ag7(DMSA)4		ESI-MS		216
Ag7	Mercaptosuccinic acid	Ag7(H2MSA)7		MALDI-MS		217
Ag8	Mercaptosuccinic acid	Ag8(H2MSA)8		MALDI-MS		217
Ag8	(3,5-Dimethyl-4-(phenyldiazenyl)-1H-pyrazole), (bis(diphenylphosphino)methane), isopropylbenzenethiol	[Ag8(iPrPhS)5(dppm)3(azopz)2]·ClO4	ClO4^−	ESI-MS		218
Ag8	Bisimidazole	Ag8K2L4(CO3)2(PF6)6		ESI-MS		219
Ag9	Iodide	Ag9I2		ESI-MS		220
Ag9	Mercaptosuccinic acid	Ag9(H2MSA)7		ESI-MS		221
Ag9	1,2-Benzenedithiolate	[Ag9(1,2-BDT)6]^3−		ESI-MS		222
Ag9–15	Glutathione	Ag9–15(SR)5–10		ESI-MS		223
Ag10	Diisopropyldithiophosphate	[Ag10{S2P(OiPr)2}8]		ESI-MS		224
Ag11	Glutathione	[Ag11(SG)7]		ESI-MS	MS/MS (SID), ion mobility	225 and 226
Ag11	Deoxyribonucleic acid	Ag11(DNA)2		ESI-MS		227
Ag12	tert-Butylthiol, trifluoroacetate	Ag12(TBT)6(TFA)6(pyz)6]·2CH3CN Ag12S2(TBT)8(TFA)4(bpy)8]·bpy		ESI-MS		228
Ag14	3,4-Difluoro-benzenethiol, triphenylphosphine	Ag14(SC6H3F2)12(PPh3)8		ESI-MS		229
Ag15	Bovine serum albumin	Ag15@BSA		MALDI-MS		230
Ag15	1,6-Bis(diphenylphosphino)hexane	[Ag15H13(DPPH)5]		ESI-MS	MS/MS (CID)	231
Ag15	Glutathione	Ag15(SG)11		ESI-MS		232
Ag16	tert-Butyl thiol, trifluoroacetate	[Ag16(TBT)8(TFA)7(CH3CN)3Cl]		ESI-MS		233
Ag16	Deoxyribonucleic acid	Ag16Cl2(DNA)2		ESI-MS		234
Ag16	Deoxyribonucleic acid	Ag16Cl2(DNA)2		ESI-MS	MS/MS (CID), ion mobility	235
Ag17	Deoxyribonucleic acid	Ag17(DNA)2		ESI-MS		236
Ag17	tert-Butyl thiol, trifluoroacetate	[Ag17(TBT)8(TFA)7(CH3CN)3Cl]		ESI-MS		233
Ag17	1-((Naphthalen-4-yl)ethyl)prop-2-yn-1-amine	[Ag17(NYA)12]^3+		ESI-MS		237
Ag17	ortho-Carboranethiol	[Ag17(o1-CBT)12]^3−		ESI-MS	MS/MS (CID)	238
Ag18	Deoxyribonucleic acid	Ag18(DNA)2		ESI-MS		239
Ag18	Triphenylphosphine	[Ag18H16(TPP)10]^2+		ESI-MS		240
Ag19	1,2-Bis(diphenylphosphino)methane, phenylacetylene	[Ag19(dppm)3(PhC≡C)14](SbF6)3	SbF6^−	ESI-MS		241
Ag20	Dithiophosphonate	[Ag20[S2P(OiPr)2]12]		ESI-MS		242
Ag21	Dithiophosphonate, 4-methoxythiophenol	[Ag21{S2P(OR)(p-C6H4OCH3)}12]PF6	PF6^−	ESI-MS		243
Ag21	Dithiophosphonate	[Ag21[S2P(OiPr)2]12]^+		ESI-MS		244
Ag21	4-tert-Butylthiacalix[4]arene	[Ag21(H2BTCA)3(O2PPh2)6]SbF6	SbF6^−	ESI-MS		245
Ag21	Deoxyribonucleic acid	Ag21(DNA)3		ESI-MS		246
Ag21	1-Ethynyl-3,5-dimethoxybenzene	[Ag21(C≡CC6H3-3,5-R2)6-(O2PPh2)10]SbF6	SbF6^−	ESI-MS		245
Ag21	4-Formylphenylethyne	[Ag21(Ph2PO2)10(p-CHOPhC≡C)6]SbF6	SbF6^−	ESI-MS		247
Ag21	9-SH meta-carboranethiol, triphenylphosphine	[Ag21(MCT)12(TPP)2]		ESI-MS	MS/MS (CID)	248
Ag22	1,2-Bis(diphenylphosphino)ethane, 2,5-dimethylbenzenethiol	Ag22(dppe)4(2,5-DMBT)12Cl4]^2+		ESI-MS		249
Ag24	tert-Butylthiol, proline	Ag24(S^tBu)10(L/D-proline)8(NO3)4(H2O)		ESI-MS		250
Ag25	2,4-Dimethylbenzenethiol	Ag25(DMBT)18		ESI-MS	MS/MS (CID)	60 and 111
Ag25	1,2-Bis(diphenylphosphino)ethane	[Ag25H22(DPPE)8]^3+		ESI-MS		240
Ag26	Tris(4-fluorophenyl)phosphine	[Ag26H22(TFPP)13]^2+		ESI-MS		240
Ag27	1,4-Bis(diphenylphosphino)butane	[Ag27H22(DPPB)7]^3+		ESI-MS	MS/MS (CID)	231
Ag28	Deoxyribonucleic acid	Ag28(DNA)2		ESI-MS		251
Ag29	1,3-Benzenedithiol, triphenylphosphine	Ag29(BDT)12(TPP)4		ESI-MS	MS/MS (CID)	111 and 252
Ag29	1,3-Benzenedithiol, fullerene	[Ag29(BDT)12(C60)n]^3−		ESI-MS	MS/MS (CID), ion mobility	253
Ag29	1,3-Benzenedithiol, triphenylphosphine	Ag29(BDT)12(TPP)4		ESI-MS	MS/MS (UVPD)	120
Ag29	Dihydrolipoic acid, 1,3-benzenedithiol	Ag29(BDT)12−x(DHLA)x		ESI-MS		133
Ag29	1,3-Benzenedithiol, 1,2-bis(diphenylphosphino) ethane	Ag29(BDT)12(dppe)4		ESI-MS		254
Ag29	Lipoic acid	Ag29(LA)19		ESI-MS	MS/MS (CID), ion mobility	255
Ag29	1,3-Benzenedithiol, 2,2′-[1,4-phenylenebis(methylidynenitrilo)]bis[benzenethiol]	[Ag29(L)12]L′4		ESI-MS	Ion mobility	136
Ag30	Captopril	Ag30(Capt)18		ESI-MS		256
Ag31	Glutathione	Ag31(SG)19		ESI-MS		232
Ag31	6-(Dibutylamino)-1,3,5-triazine-2,4-dithiol	Ag31(TRZ)10		ESI-MS		257
Ag31	Glutathione	Ag31(SG)19		ESI-MS		258
Ag32	Glutathione	Ag32(SG)19		ESI-MS		259
Ag32	N-(2-Mercaptopropionyl)glycine	Ag32(MPG)19		ESI-MS, MALDI-MS		260
Ag33	4-tert-Butylthiacalix[4]arene, cyclohexanethiol	Ag33(TC4A)4(CyS)10		ESI-MS		261
Ag34	3,3-Dimethyl-1-butyne	Ag34(^tBuC≡C)24(CH3COO)2	CH3COO^−	ESI-MS		262
Ag34	4-tert-Butylbenzyl mercaptan	Ag34S3SBB20(CF3COO)6^2+		ESI-MS		263
Ag35	3,3-Dimethyl-1-butyne, 4-tert-butylthiacalix[4]arene	[Ag35(H2L)2(L)(C≡CBut)16]^3+		ESI-MS		264
Ag37	Trifluoroacetate, tert-butylbenzenethiol	[Ag37S4(SC6H4^tBu)24(CF3COO)6(H2O)12]^−		ESI-MS		265
Ag39	Pentafluorobenzenethiol, triphenylphosphine	[Ag39(PFBT)24(TPP)8]^2−		ESI-MS		266
Ag40	1,7-Bis(mercapto)-m-carborane, triphenylphosphine	Ag40(C2B10H10S2)12(PPh3)8		ESI-MS		69
Ag40	2,4-Dimethylbenzenethiol	[Ag40(2,4-DMBT)24(PPh3)8]		ESI-MS		267
Ag40	Dimethylbenzenethiol, triphenylphosphine	[Ag40(SPhMe2)24(PPh3)8](NO3)2		ESI-MS	MS/MS (CID)	268
Ag42	o-Carborane-1,2-dithiol, triphenylphosphine	[Ag42(CBDT)15(TPP)4]^2−		ESI-MS	MS/MS (CID)	269
Ag42	6-(Dibutylamino)-1,3,5-triazine-2,4-dithiol	Ag42(TRZ)13		ESI-MS	MS/MS (CID)	257
Ag42	4-tert-Butylthiacalix[4]arene	Ag42(MoO3-TC4A)6(EtS)14(CH3CN)5Cl		ESI-MS		270
Ag44	4-tert-Butylthiacalix[4]arene	Ag44(BTCA)6		ESI-MS		271
Ag44	5-Mercapto-2-nitrobenzoic acid	[Ag44(MNBA)30]^4−		ESI-MS		272
Ag44	4-Mercaptobenzoic acid	Na4Ag44(MBA)30		ESI-MS		273
Ag44	2-Ethylbenzenethiolate, triphenylphosphine	Ag44(EBT)26(TPP)4		MALDI-MS		274
Ag44	Benzeneselenol	[Ag44(SePh)30]^4−		ESI-MS		275
Ag44	Benzeneselenol	[Ag44(SePh)30]^4−		MALDI-MS		276
Ag44	4-Mercaptobenzoic acid	M4Ag44(MBA)30		ESI-MS		277
Ag44	3,4-Difluorobenzenethiolate	[Ag44(SC6H3F2)30]^4−		ESI-MS	Mass-selected PES	145
Ag44	4-Fluorothiophenol	Ag44(4-FTP)30		ESI-MS	MS/MS (CID), ion mobility	40, 111 and 278
Ag46	2,4-Dimethylbenzenethiol, triphenylphosphine	[Ag46(SPhMe2)24(PPh3)8](NO3)2		ESI-MS		268
Ag47	3,3-Dimethyl-1-butyne, L-/D-valine, L-/D-isoleucine	[Ag47L12(C≡C^tBu)16]BF4	BF4^−	ESI-MS		279
Ag48	3,3-Dimethyl-1-butyne	[Ag48(C≡CtBu)20(CrO4)7]	CrO4^−	ESI-MS		280
Ag48	1-Adamantanethiol, cyclohexanethiol	Ag48Cl14(S-Adm)26(S-c-C6H11)4		ESI-MS		281
Ag50	1,3-Bis(diphenylphosphino) propane, 1-adamantanethiol	Ag50Cl16(S-Adm)28(dppp)2		ESI-MS		250
Ag50	1,1-Bis(diphenylphosphino) methane	Ag50(dppm)6(SR)30		ESI-MS		282
Ag52	Isopropylmercaptan	Ag52(^iPrS)25(CF3COO)16(H2O)3(CH3OH)2]		ESI-MS		283
Ag52	N,N′-Di(5-fluoro-2-pyridinyl)formamidine	[Ag52(5-F-dpf)16Cl4](SbF6)2	SbF6^−	ESI-MS		284
Ag53	N,N′-Di(5-methyl-2-pyridinyl)formamidine	[Ag53(5-Me-dpf)18](NO3)5	NO3^−	ESI-MS		284
Ag54	4-tert-Butylthiacalix[4]arene, cyclohexanethiol	Ag54(TC4A)6(CyS)11(OAc)4(CH3CN)2Cl	Cl^−	ESI-MS		261
Ag55	4-tert-Butylbenzylthiol, phenylethanethiol	Ag55(SR)31		ESI-MS, MALDI-MS		285
Ag58	Trifluoroacetic acid, isopropylthiophenol	Ag58(^iPrC6H4S)40(CF3COO)6(H2O)10		ESI-MS		286
Ag59	2,5-Dichlorobenzenethiol	[Ag59(2,5-DCBT)32]^3−		ESI-MS		287
Ag60	tert-Butylthiol	[Ag60(^tBuS)20(o-CH3OPhCOO)16(H2O)4(Cl)2]	Cl^−	ESI-MS		288
Ag61	Dipyridylamine	Ag61(dpa)27(SbF6)4	SbF6^−	ESI-MS		70
Ag67	2,4-Dimethylbenzenethiol, triphenylphosphine	[Ag67(SPhMe2)32(PPh3)8]^3+		ESI-MS		62
Ag68	4-tert-Butylbenzylmercaptan	Ag68(SBB)34		MALDI-MS		289
Ag71	1,1-Bis-(diphenylphosphino)methane, tert-butylthiol	[Ag71(S-Bu)31(dppm)](SbF6)2	SbF6^−	ESI-MS		290
Ag74	Phenylacetylene	Ag74(C≡CPh)44		ESI-MS		71
Ag74	2-Methylphenylacetylene	Ag74(2-CH3C6H4C≡C)44		ESI-MS		291
Ag75	Glutathione	Ag75(SG)40		ESI-MS		292
Ag78	1,1-Bis-(diphenylphosphino)methane	[Ag78(^iPrPhS)30(dppm)10Cl10]^4+	Cl^−	ESI-MS		293
Ag86	2-Methylphenylacetylene	Ag86(2-CH3C6H4C≡C)50		ESI-MS		291
Ag88	4-tert-Butylthiacalix[4]arene	Ag88(TC4A)8(EtS)32(OAc)8(CH3CN)		ESI-MS		294
Ag93	4-Methoxyphenylacetylene	Ag93(PPh3)6(C≡CR)50		ESI-MS		295
Ag98	2-Methylphenylacetylene	Ag98(2-CH3C6H4C≡C)52		ESI-MS		291
Ag110	2-Fluorothiophenol, triphenylphosphine	Ag110(SPhF)48(PPh3)12		MALDI-MS		296
Ag112	3,5-Trifluoromethylphenylacetylene	[Ag112Cl6(3,5-(CF3)2PhC≡C)51]^3−		ESI-MS		297
Ag123	tert-Butyl thiol	[Ag123S35(S^tBu)50]		MALDI-MS		298
Ag136	4-tert-Butylbenzenethiol	[Ag136(SR)64Cl3Ag0.45]^−		ESI-MS		299
Ag140	4-tert-Butylbenzylmercaptan	Ag140BBT53		MALDI-MS		300
Ag141	Adamantanethiol	[Ag141X2(S-Adm)40]^3+		ESI-MS		61
Ag146	4-Isopropylbenzenethiolate	Ag146Br2(SR)80		ESI-MS		32
Ag152	Phenylethanethiol	Ag152(SCH2CH2Ph)60		MALDI-MS		301
Ag154	1,4-Bis-(diphenylphosphanylmethyl)benzene	[Ag154Se77(Dppxy)18]		MALDI-MS		302
Ag213	Adamantanethiol	Ag213(Adm-S)44Cl33		ESI-MS		303
Ag280	4-tert-Butylbenzylmercaptan	Ag280(SBB)120		ESI-MS		53
Ag320	1,1-Bis(diphenylphosphino)propane, tert-butyl thiol	[Ag320S130(S^tBu)60(dppp)12]		MALDI-MS		302
Ag344	tert-Butyl thiol	[Ag344S124(S^tBu)96]		MALDI-MS		298
Ag352	tert-Butyl thiol	[Ag352S128(StC5H11)]		MALDI-MS		302
Ag374	4-tert-Butylbenzenethiol	[Ag374(SR)113Br2Cl2]		ESI-MS		299
Ag490	tert-Butyl thiol	[Ag490S188(S^tC5H11)114]		MALDI-MS		302
Au5	Triphenylphosphine	Au5(PPh3)5]^+		ESI-MS		304
Au6	1,3-Bis(diphenylphosphino) propane	[Au6(dppp)4]^2+		ESI-MS		305
Au6	Polyethylene glycol, biotin	Au6(S-PEG70-biotin)6		ESI-MS		306
Au7	Polyethylene glycol, biotin	Au7(S-PEG70-biotin)7		ESI-MS		306
Au9	Dibenzimidazolium salt	[Au9(NHC)4Br]Br2	Br^−	ESI-MS		307
Au9	2,6-Bis(1-(diphenylphosphaneyl)ethyl)pyridine	Au9(PNP)6		ESI-MS		308
Au10	Mercaptosuccinic acid	Au10(MSA)6		MALDI-MS		309
Au10	tert-Butylbenzenethiol	Au10(TBBT)10		MALDI-MS		310
Au10	Polyethylene glycol	Au10(S-PEG12-CO2H)10		ESI-MS		306
Au10	Dibenzimidazolium salt	[Au10(NHC)4Br2](O2CCF3)2		ESI-MS		307
Au10	Polyethylene glycol, biotin	Au10(S-PEG70-biotin)10		ESI-MS		306
Au10	1,3-Di(2,4,6-trimethylbenzyl)benzimidazolium halide	[Au10(MesCH2Bimy)6X3]		ESI-MS		311
Au11	3-Mercaptopropionic acid	Au11(SCH2CH2COOH)7(TOA)7	TOA^+	ESI-MS		312
Au11	1,3-Bis(diphenylphosphino)propane	[Au11(dppp)5]^3+		ESI-MS		305
Au11	DPEphos	[Au11(DPEphos)4Cl2]Cl	Cl^−	ESI-MS		313
Au11	Polyethylene glycol	Au11(SPEG12-CO2H)11		ESI-MS		306
Au11	Xantphos	[Au11(Xantphos)4Cl2]Cl	Cl^−	ESI-MS		313
Au11	Diphosphine	[Au11(DP)4L2]^+		ESI-MS		314
Au11	Triphenylphosphine (X = chloride or phenylacetylene)	[Au11(PPh3)8X2]^+		ESI-MS	MS/MS (CID)	315
Au12	Polyethylene glycol	Au12(S-PEG12-CO2H)12–14		ESI-MS		306
Au13	1,2-Bis(diphenylphosphino)ethane	[Au13(dppe)5Cl2]Cl3	Cl^−	ESI-MS		316
Au13	1,3-Bisubstituted benzimidazolium chloride	[Au13(NHC)10Cl2]^3+		ESI-MS		317
Au13	1,3-Disubstituted benzimidazolium chloride	[Au13(NHC)5Cl2]Cl3	Cl^−	ESI-MS		72
Au14	1,3-Bis(diphenylphosphinopropane)	Au14(dppp)5I4	Cl^−	ESI-MS		318
Au15	Glutathione	Au15(SG)13		ESI-MS		54
Au15	Glutathione, cyclodextrin	Au15@CD		ESI-MS		319
Au15	Glutathione	Au15(SG)13		ESI-MS		320
Au16	1-Adamantanethiol	Au16(S-Adm)12		ESI-MS		321
Au18	Glutathione	Au18(SG)14		ESI-MS		322
Au18	Glutathione, Thiol-17mer	Au18(SG)13-17mer		ESI-MS		323
Au18	Glutathione	Au18(SG)14		ESI-MS		324
Au18	Cyclohexanethiol	Au18(SC6H11)14		ESI-MS		325
Au18	2,4,6-Triisopropylbenzylmercaptan	Au18S2-(STipb)12		ESI-MS		326
Au18	3-Mercaptopropionic acid	Au18(SC2H4CO2H)14		MALDI-MS		327
Au19	N,N-Bis(diphenylphosphino)amine, phenylacetylene	[Au19(PhC≡C)9(Hdppa)3](SbF6)2	SbF6^−	ESI-MS		328
Au19	Phenylethanethiol	Au19(SC2H4Ph)13		ESI-MS		329
Au20	4-Pyridinethanethiol	Au20(4-PyET)14CN		MALDI-MS		330
Au20	1-Adamantanethiol, diphenyl-2-pyridylphosphine	Au20(AdmS)14(PhPy2P)		ESI-MS		331
Au20	Triphenylphosphine	[Au20(PPh3)4]		ESI-MS		332
Au20	Tris(2-(diphenylphosphino) ethyl)phosphine	[Au20(dppp3)4]Cl4	Cl^−	ESI-MS		73
Au21	1-Adamantanethiol, tris(4-fluorophenyl)phosphine	Au21(AdmS)13S(F3Ph3P)		ESI-MS		331
Au21	3-Methylbenzenethiol, N,N-bis(diphenylphosphino)amine	Au21(m-MBT)12(Hdppa)2		ESI-MS		333
Au22	Cysteinyl-lysyl-cysteine	Au22(Lys–Cys–Lys)16		ESI-MS		334
Au22	Glutathione, porphyrin	Au22[(SG)15(SAOPPTH2)2]		MALDI-MS		335
Au22	1,8-Bis-(diphenylphosphino)octane	Au22(L)6		ESI-MS		336
Au22	Glutathione, boric acid	Au22(SG)18		MALDI-MS		337
Au22	Glutathione	Au22(SG)18		ESI-MS		338
Au22	3-Ethynylthiophene, phenylacetylene, 3-ethynyltoluene, 3-ethynylanisole	Au22(C≡CPh)18		MALDI-MS		74
Au22	Dimethylaminobenzenethiol	Au22(DMAT)15H		ESI-MS		339
Au22	1,2-Bis-(diphenylphosphino)ethane, triphenylphosphine, hydride	Au22H3(dppe)3(PPh3)8		ESI-MS		340
Au22	Bis(2-diphenylphosphino)ethyl ether, hydride	Au22H3(dppee)7		ESI-MS	Ion mobility	341
Au23	Cyclohexanethiol	[Au23(SC6H11)16]^−		MALDI-MS		342
Au23	Glutathione	Au23(SG)18		MALDI-MS		343
Au23	Cyclohexanethiol	[Au23(SC6H11)16]^−		ESI-MS		344
Au23	3,3-Dimethyl-1-butyne	Au23(C≡C^tBu)15		MALDI-MS		345
Au23	Phenylethanethiol, 4-tert-butylbenzenethiol	Au23(SPh^tBu)17		ESI-MS, MALDI-MS		346
Au24	Phenylethanethiol, triphenylphosphine	[Au24(PPh3)10(SC2H4Ph)5X2]^+		ESI-MS		347
Au24	Benzene selenol	Au24(SePh)20		ESI-MS		348
Au24	Adamantanethiol	Au24(SAdm)16		ESI-MS		56
Au24	Polyvinyl 2-pyrrolidone (PVP)	Au24Clx (x = 0–3)		MALDI-MS		349
Au25	Glutathione	Au25(SG)18		ESI-MS		350
Au25	Triphenylphosphine, alkanethiol	[Au25(PPh3)10(SCnH2n+1)5Cl2]^2+	Cl^−	ESI-MS		351
Au25	Hexanethiol	Au25(SC6H13)18		ESI-MS		352
Au25	Glutathione	Au25(SG)18		ESI-MS		353
Au25	Glutathione	Au25(SG)18		ESI-MS		354
Au25	Phenylethanethiol	Au25(SCH2CH2Ph)18^−		ESI-MS		355
Au25	Phenylethanethiol	Au25(SCH2CH2Ph)18		ESI-MS		356
Au25	Glutathione	Au25(SG)18		MALDI-MS		357
Au25	Phenylethanethiol	Au25(SCH2CH2Ph)18		ESI-MS		358
Au25	Glutathione	[Au25(SG)18 − 6H]^7−		ESI-MS	MS/MS (CID), action spectroscopy	144
Au25	Phenylethanethiol	[Au25(SCH2CH2Ph)18]-		ESI-MS	MS/MS (CID), ion mobility	109
Au25	Phenylethanethiol	[Au25(SCH2CH2Ph)18]-		MALDI-MS, FAB-MS		359 and 360
Au25	Dioctyl diselenide	Au25(SeC8H17)18		ESI-MS		361
Au25	Dodecanethiol	Au25(SC12H25)18		MALDI-MS		362
Au25	Ethanethiol	Au25(SC2H5)18		MALDI-MS		363
Au25	para-Mercaptobenzoic acid	Au25(pMBA)18		ESI-MS	MS/MS (CID), MS/MS (UVPD)	117
Au25	Cysteine	Au25(Cys)18		ESI-MS		364
Au25	Glutathione	Au25(SG)18		MALDI-MS		365
Au25	Glutathione	Au25(SG)18		ESI-MS		366
Au25	4-Mercapto-n-butoxycalix[4]arene	[Au25(Calix-4S)18]		ESI-MS		367
Au25	Butanethiol	Au25(BT)18		MALDI-MS		368
Au25	6-Mercaptohexanoic acid	Au25(MHA)18		ESI-MS		369
Au25	2-Methacryloyloxyethyl, phosphorylcholine	Au25(MPC)18		ESI-MS		370
Au25	4-tert-Butylbenzyl mercaptan	Au25(SBB)18		ESI-MS, MALDI-MS		371
Au25	Phenylethanethiol	[Au25(PET)18(O2)n]^−		ESI-MS		372
Au25	(R)-5,5′,6,6′,7,7′,8,8′-Octafluoro-[1,1′-binaphthalene]-2,2′-dithiol	Au25(R-BINAS)18		MALDI-MS		373
Au25	2-Phenylethanethiol, triphenylphosphine	Au25(PPh3)10(SC2H4Ph)5Cl2	Cl^−	ESI-MS	MS/MS (UVPD)	121
Au25	(1R,1′R)-6,6′-(1,4-Phenylene)di-1,1′-binaphthyl-2,2′-dithiol	Au25(PET)14(BINAS)2		MALDI-MS		374
Au25	4-Mercaptobenzoic acid, arginylglycylaspartic acid	Au25(pMBA)18−x(cRGD)x		ESI-MS		375
Au25	Diphenyl-2-pyridylphosphine, N,N-diethyldithiocarbamate	Au25(DETC)5(DPPY)10Cl2	Cl^−	ESI-MS		376
Au25	Cysteine	Au25(Cys)18		ESI-MS		377
Au25	4-Mercaptobenzoic acid, Thiol-17mer	Au25(pMBA)(18−n)17mer(n)		ESI-MS		323
Au26	1,3-Diisopropylimidazole, N,N′-di(3,4-dimethyl-phenyl)formamidine	Au26(3,4-Me2-Phform)9(^iPr2-imy)3(Me2S)		ESI-MS		378
Au28	Glutathione	Au28(SG)14		ESI-MS		379
Au28	Glutathione	Au28(SG)14		MALDI-MS		53
Au28	4-Methylbenzenethiol, N,N-bis(diphenylphosphino)amine	Au28(p-MBT)14(Hdppa)3		ESI-MS		333
Au28	2-Phenylpropane-1-thiol	Au28(PPT)21		ESI-MS		380
Au28	4-tert-Butylphenylacetylene	Au28(^tBuC6H4C≡C)20		ESI-MS		381
Au28	N,N′-Diphenylformamidinate	[Au28(Ph-form)12](OTf)2		ESI-MS		382
Au28	9-HC≡C-closo-1,2-C2B10H11, tetrahydrothiophene	[Au28(C4B10H11)12(tht)8]^3+		ESI-MS		383
Au28	tert-Butylbenzenethiol	Au28(SCH2Ph-^tBu)22		ESI-MS		384
Au29	Glutathione	Au29(SG)18		ESI-MS		385
Au30	Adamantanethiol	Au30(SAd)18		MALDI-MS		386
Au30	tert-Butyl thiol	Au30(S-^tC4H9)18		ESI-MS, MALDI-MS		387
Au30	tert-Butyl thiol	Au30S(S-^tC4H9)18		ESI-MS		388
Au34	Phenylacetylene, triphenylphosphine	Au34(PhC≡C)14(Ph3P)6		ESI-MS		389
Au36	Thiophenol	Au36(SPh)23		MALDI-MS		390
Au36	4-tert-Butylbenzenethiol	Au36(SPh-^tBu)24		ESI-MS		391
Au36	para-Mercaptobenzoic acid	Au36(pMBA)24		ESI-MS	MS/MS (CID), MS/MS (UVPD)	117
Au36	Naphthalenethiol	Au36(NT)24		MALDI-MS		392
Au36	4-Methylthiophenol	Au36(MTP)24		ESI-MS		393
Au36	Phenylacetylene	Au36(C≡CPh)24		MALDI-MS		394
Au37	4-tert-Butylbenzenethiol, triphenylphosphine	Au37(TBBT)21(TPP)2		ESI-MS		395
Au38	Alkanethiol	Au38(SR)24		ESI-MS		396
Au38	Alkanethiol	Au38(SR)24		MALDI-MS		397
Au38	Dodecanethiol	Au38(SC12H25)24		ESI-MS, MALDI-MS		398
Au38	2-Phenylethanethiol	Au38(SCH2CH2Ph)24		MALDI-MS		399
Au38	2-Phenylethanethiol	Au38(SCH2CH2Ph)24		MALDI-MS		400
Au38	2-Phenylethanethiol	Au38(SCH2CH2Ph)24		MALDI-MS		401
Au38	2-Phenylethanethiol	Au38(SCH2CH2Ph)24		MALDI-MS		402
Au38	Hexanethiol	Au38(SC6H13)24		MALDI-MS		403
Au38	Hexanethiol	Au38(SC6H13)24		MALDI-MS		404
Au38	Dodecanethiol	Au38(SC12H25)24		MALDI-MS		405
Au40	2-Phenylethanethiol	Au40(SCH2CH2Ph)24		MALDI-MS		406
Au40	2-Phenylethanethiol	Au40(SCH2CH2Ph)24		MALDI-MS		407
Au40	2-Phenylethanethiol	Au40(SCH2CH2Ph)24		MALDI-MS		399
Au40	2-Phenylethanethiol	Au40(SCH2CH2Ph)24		MALDI-MS		401
Au40	4-tert-Butylbenzenethiol, 1,2-bis(diphenylphosphine)benzene	Au40(TBBT)24(dppbe)		ESI-MS		408
Au41		Au41(S-Eind)12		MALDI-MS		409
Au42	4-tert-Butylbenzenelthiol	Au42(Ph^tBu)26		ESI-MS		410
Au42	5-Trifluoropyridyl-2-amine, triphenylphosphine	Au42(Ph3P)10(5-CF3-Hpa)8		ESI-MS		411
Au42	2-(Trifluoromethyl)phenylacetylene	Au42(C≡CC6H4-2-CF3)22		MALDI-MS		412
Au43	Phenylacetylene	Au43L22		MALDI-MS		413
Au44	4-tert-Butylbenzenelthiol	Au44(TBBT)28		ESI-MS		408
Au44	2,4-Dimethylbenzenethiol	Au44(2,4-DMBT)26		ESI-MS		83
Au44	Phenylacetylene	Au44(C≡CPh)28		MALDI-MS		394
Au49	2,4-Dimethylbenzenethiol	Au49(2,4-DMBT)27		ESI-MS		414
Au50	3-(Trifluoromethyl)phenylacetylene	Au50(C≡CC6H4-3-F)26		MALDI-MS		412
Au54	Phenylacetylene	Au54(C≡CPh)26		MALDI-MS		415
Au54	Phenylacetylene	Au54(C≡CPh)26		MALDI-MS		413
Au55	Octadecanethiol	Au55(SC18)32		MALDI-MS		416
Au55	Octadecanethiol	Au55(SC18)32		MALDI-MS		417
Au55	Phenylethanethiol	Au55(SCH2CH2Ph)31		ESI-MS		418
Au55	4-Methylbenzenethiolate, triphenylphosphine	[Au55(p-MBT)24(Ph3P)6](SbF6)3	SbF6^−	ESI-MS		419
Au60	Triphenylphosphine, benzeneselenol	[Au60Se2(Ph3P)10(SeR)15]^+		MALDI-MS		420
Au64	Cyclohexanethiol	Au64(S-c-C6H11)32		ESI-MS, MALDI-MS		421
Au65	Cyclohexanethiol	Au65(SCy)30		MALDI-MS		386
Au67	Hexanethiol	Au67(SR)35		MALDI-MS		422
Au67	3-Mercaptopropionsulfonic acid	Au67(MPSA)35		ESI-MS		423
Au68	Phenylethanethiol	Au68(SCH2CH2Ph)34		MALDI-MS		424
Au75	Hexanethiol	Au75(SC6H13)40		MALDI-MS		425
Au76	4-(2-Mercaptoethyl)benzoic acid	Au76(4-MEBA)44		ESI-MS		426
Au78	4-tert-Butylbenzenelthiol	Au78(TBBT)40		ESI-MS		427
Au82	3-Mercaptopropionsulfonic acid	Au82(MPSA)44		ESI-MS		376
Au92	4-tert-Butylbenzenelthiol	Au92(TBBT)44		ESI-MS		428
Au92	4-tert-Butylbenzenelthiol	Au92(TBBT)44		ESI-MS		429
Au99	2,4-Difluorophenylacetylene	Au99(C≡CC6H3-2,4-F2)40		MALDI-MS		430
Au99	Thiophenol	Au99(SPh)42		ESI-MS, MALDI-MS		431
Au100	Naphthalenethiol	Au100(Napt)42		ESI-MS, MALDI-MS		432
Au102	4-Mercaptobenzoic acid	Au102(pMBA)44		ESI-MS, MALDI-MS		433
Au102	4-Mercaptobenzoic acid	Au102(pMBA)44		ESI-MS		434
Au102	Thiophenol	Au102(SPh)44		ESI-MS, MALDI-MS		435
Au102	Isopropyl benzenethiol	Au102(IPBT)44		ESI-MS, MALDI-MS		433
Au102–104	4-tert-Butylbenzenelthiol	Au102–104(TBBT)44–46		ESI-MS, MALDI-MS		436
Au103	Naphthalenethiol	Au103S2(S-Nap)41		ESI-MS		437
Au103–105	Phenylethanethiol	Au103–105(CH2CH2Ph)45–46		ESI-MS		438
Au106	3,5-Bis(trifluoromethyl)phenylacetylene	[Au106L40Cl12][HNEt3]4		ESI-MS		439
Au110	4-(Trifluoromethyl)phenylacetylene	[Au110(4-CF3C6H4C≡C)48] [HNEt3]2	HNEt3^+	ESI-MS		440
Au110	Phenylpentyne	Au110(C≡CC3H6Ph)48		ESI-MS		75
Au126	4-tert-Butylbenzenethiol	Au126I4(TBBT)4		ESI-MS		441
Au127	4-tert-Butylbenzenethiol	Au127I4(TBBT)4		ESI-MS		441
Au130	4-Bromothiophenol	Au130(SPh-Br)50		MALDI-MS		442
Au130	Dodecanethiol	Au130(SC12H25)50		ESI-MS, MALDI-MS		443
Au130	2-Flurophenylacetylene	Au130(C≡CR)50		MALDI-MS		444
Au130	Dodecanethiol	Au130(SR)50		ESI-MS		445
Au130	Phenylethanethiol	Au130(SR)50		MS/MS (CID)		110
Au133	4-tert-Butylbenzenethiol	Au133(TBBT)52		ESI-MS, MALDI-MS		65
Au133	4-tert-Butylbenzenethiol	Au133(TBBT)52		ESI-MS		66
Au137	Dodecanethiol	Au137(SC12H25)56		MALDI-MS		446
Au137	Phenylethanethiol, hexanethiol	Au137(SR)56		ESI-MS		447
Au138	2,4-Dimethylbenzenethiol	Au138(SR)48		ESI-MS		448
Au144–146	Butanethiol, hexanethiol, octanethiol	Au144–146(SR)50–60		LDI-MS		449
Au144	2-Flurophenylacetylene	Au144(2-FC6H4C≡C)60		MALDI-MS		450
Au144	2-Phenylethanethiol, hexanethiol, butanethiol	Au144(SR)60		ESI-MS, MALDI-MS		451
Au144	Phenylacetylene	Au144(PhC≡C)60		ESI-MS		452
Au145	Butanethiol, pentanethiol	Au145(SR)60X (X = Br, Cl)	X^−	ESI-MS		453
Au146	4-Mercaptobenzoic acid	Au146(pMBA)57		ESI-MS		454
Au156	4-(Trifluoromethyl)phenylacetylene	Au156(4-CF3C6H4C≡C)60		ESI-MS		455
Au187	Dodecanethiol	Au187(SC12H25)68		ESI-MS, MALDI-MS		445
Au191	4-tert-Butylbenzenethiol	Au191(TBBT)66		ESI-MS		456
Au246	4-Methylbenzenethiol	Au246(pMBT)80		ESI-MS, MALDI-MS		457
Au329	Phenylethanethiol	Au329(SCH2CH2Ph)84		ESI-MS, MALDI-MS		458
Au333	Phenylethanethiol	Au333(SR)79		ESI-MS, MALDI-MS		64
Au333	Hexanethiol	Au333(SR)79		MALDI-MS		459
Au∼500	Phenylethanethiol, hexanethiol	Au∼500(SR)∼120		ESI-MS, MALDI-MS		94
Au∼940	Phenylethanethiol, hexanethiol	Au∼940±20(SR)∼160±4		ESI-MS, MALDI-MS		95
Au∼1400	Phenylethanethiol, hexanethiol	Au∼1400(SR)∼240		MALDI-MS		96
Au∼2000	Phenylethanethiol, hexanethiol	Au∼2000(SR)∼290		MALDI-MS		97
Cu4	2-Mercaptobenzimidazole	Cu4(C7H5N2S)4		ESI-MS	IM-MS	460
Cu4	1,2-Bis(diphenylphosphino)ethane, 2-mercaptonicotinic acid	[Cu4(MNA)2(DPPE)2]		MS/MS (CID)		461
Cu6	2-Mercaptonicotinic acid	[Cu6(MNA)6]		MS/MS (CID)		461
Cu6	2-Mercaptobenzoxazole	Cu6(SR)6		ESI-MS		462
Cu6	Glutathione	Cu6(GS)2		MALDI-MS		463
Cu6	Triphenylphosphine, benzeneselenol	[Cu6(SePh)6(PPh3)3(4,4′-bpy)]		ESI-MS		464
Cu6	Dithiophosphinate	Cu6[μ3-S2P(OEt)2]6		ESI-MS		465
Cu6	2-Mercaptobenzimidazole	Cu6H(C7H5N2S)6		IM-MS		463
Cu6	Diphenylethylphosphine, benzenetellurol	[Cu6(TePh)6(PEtPh2)5]		ESI-MS		466
Cu7	4-Chlorothiophenol, triphenylphosphine	Cu7L4(PPh3)3		ESI-MS		467
Cu8	4-Hydroxy-6-(trifluoromethyl) pyrimidine-2-thiol, 1,2-bis(diphenylphosphino)ethane	[Cu8(TFMPT)4(DPPE)4]		ESI-MS		468
Cu8	4-Aminobenzenethiol, triphenylphosphine	Cu8(m-ABT)8-[P(PhPF)3]4		ESI-MS		469
Cu8	4-Methylbenzenethiol, triphenylphosphine	Cu8(p-MBT)8(PPh3)4		ESI-MS		469
Cu8	4-tertButylbenzenethiol, triphenylphosphine	Cu8(TBBT)8(PPh3)4		ESI-MS		469
Cu8	Triphenylphosphine	[Cu8Te4(PPh3)7]		ESI-MS		470
Cu11	N,N′-Di(5-trifluoromethyl-2-pyridyl)formamidinate, hydride	Cu11H3(Tf-dpf)6(OAc)2	OAc^−	ESI-MS		471
Cu11	4-Chlorothiophenol, triphenylphosphine	Cu11L5(PPh3)3		ESI-MS		467
Cu12	N,N′-Di(5-trifluoromethyl-2-pyridyl)formamidinate, hydride	[Cu12H3(Tfdpf)6(OAc)2]	OAc^−	ESI-MS		471
Cu12	1,8-Bis(diphenylphosphino)octane	Cu12S6(dppo)4		MALDI-MS		472
Cu12	Triethylphosphine, benzenetellurol	[Cu12Te3(TePh)6(PEt3)6]		ESI-MS		473
Cu12	Triethylphosphine	[Cu12S6(PEt3)8]		ESI-MS		474
Cu14	o-9,12-Carboranedithiol	[Cu14(S2C2B10H10)6]		ESI-MS	MS/MS (CID)	475
Cu14	1,3-Dimercaptopropane, triphenylphosphine	[Cu14(DMP)6(PPh3)H]		ESI-MS		476
Cu14	Isopropylthiol, triphenylphosphine	[Cu14(iPrS)3(PPh3)8H10]		ESI-MS		477
Cu14	Glutathione	Cu14(SG)12		ESI-MS		478
Cu15	2-Phenylethanethiol, triphenylphosphine	[Cu15(PPh3)6(PET)13]^2+		ESI-MS		479
Cu15	2-Phenylethanethiol, triphenylphosphine	[Cu15(PhCH2CH2S)13(PPh3)6][BF4]2	BF4^−	ESI-MS		480
Cu16	1,2-Bis-(diphenylphosphino)ethane, dimercaptomaleonitrile	[Cu16(Se)6(DPPE)4(MNT)2]		ESI-MS		481
Cu18	2-Phenylethanethiol, triphenylphosphine	Cu18(PET)16(PPh3)4Cl	Cl^−	ESI-MS		76
Cu18	2-Phenylethanethiol, triphenylphosphine	[Cu18H(PhCH2CH2S)14(PPh3)6Cl3]		ESI-MS		480
Cu20	Triphenylphosphine	[Cu20S10(PPh3)8]		ESI-MS		474
Cu20	N,N′-Di(5-trifluoromethyl-2-pyridyl)formamidinate, hydride	[Cu20H8(Tf-dpf)10]·(BF4)2	BF4^−	ESI-MS		482
Cu23	4-Toluenethiol, triphenylphosphine	Cu23H4(SC7H7)18(PPh3)6		ESI-MS		483
Cu23	Triphenylphosphine	[Cu23(PhSe)16(Ph3P)8(H)6]·BF4	BF4^−	ESI-MS		484
Cu25	Triphenylphosphine	[Cu25H22(PPh3)12]Cl	Cl^−	ESI-MS		485
Cu26	Dimercaptomaleonitrile, 1,2-bis-(diphenylphosphino)ethane	Cu26(Se)12(DPPE)6		ESI-MS		481
Cu27	Dithiocarbamate, hydride	Cu27H15{S2CNnBu2}12		ESI-MS		486
Cu31	1,2-Bis(diphenylphosphino)ethane, 4-Methoxyphenylacetylene	Cu31(4-MeO-PhC≡C)21(dppe)3		ESI-MS		487
Cu32	2-Phenylethanethiol	Cu32(PET)24H8Cl2	Cl^−	ESI-MS		488
Cu32	Phenylethanethiol, hydride	[Cu32(PET)24H8Cl2](PPh4)2	PPh4^+	ESI-MS		489
Cu33	N,N′-Di(5-methyl-2-pyridinyl)formamidine, hydride	Cu33H18(Medpf)12, Cu33H16(Medpf)12Cl2		ESI-MS		77
Cu32–34	Phenylethanethiol, hydride	[Cu32(PET)24H8Cl2](PPh4)2	PPh4^+	ESI-MS		490
Cu36	2-(2-(Diphenylphosphaneyl)-phenethyl)quinoline, 1-adamantanethiol	Cu36L7(S-Adm)3(OAc)	OAc^−	ESI-MS		491
Cu38	Phenylphosphinic acid, 1-ethynyl-1-cyclohexanol	Cu38(C2)4(HOchxC≡C)22(PhHPO2)2(PhPO3)2(CH3OH)		ESI-MS		492
Cu41	2-Fluorothiophenol, triphenylphosphine, hydride	Cu41Cl2(2-F-C6H4S)12(CF3COO)6(PPh3)6H19		ESI-MS		493
Cu47	Benzene selenol, triphenylphosphine, hydride	Cu47(PhSe)15(PPh3)5(CF3COO)12H12		ESI-MS		494
Cu50	4-Fluorothiophenol, triphenylphosphine, hydride	Cu50(CF3COO)10(4-F-PhS)20(PPh3)6H2		ESI-MS		495
Cu50	Diphenylethylphosphine, TePh	[Cu50Te17(TePh)20(PEtPh2)8]		ESI-MS		466
Cu54	2-Methyl-2-propanethiol	Cu54XCl12(^tBuS)20(NO3)12		ESI-MS		487
Cu61	4-tert-Butylbenzenethiol	Cu61(StBu)26S6Cl6H14		ESI-MS		496
Cu75	Adamantanethiol	Cu75(S-Adm)32		ESI-MS		78
Cu81	4-tert-Butylbenzenethiol	[Cu81(PhS)46(^tBuNH2)10(H)32]^3+		ESI-MS		497
Cu93	Triphenylphosphine	[Cu93Se42(SeC6H4SMe)9(PPh3)18]		MALDI-MS		498
Cu96	Triphenylphosphine	[Cu96Se45(SeC6H4SMe)6(PPh3)18]		MALDI-MS		498
Cu136	1,5-Bis-(diphenylphosphino)pentane	[Cu136S56(SCH2C4H3O)24(Dpppt)10]		MALDI-MS		498
Ir9	Phenylethanethiol	Ir9(PET)6		MALDI-MS		82
Ir50	Phenylacetylene	Ir50(PA)25		ESI-MS		499
Pd7	Ketimide	Pd7(N=C^tBu2)6		ESI-MS		500
Pd8	Adamantanethiol, triphenylphosphine	Pd8(PPh)2PPh3(S-Adm)6		ESI-MS		501
Pd21	Phenylethanethiol	Pd21(SCH2CH2Ph)18		ESI-MS		79
Pd38	Phenylethanethiol	Pd38(SCH2CH2Ph)21S2		ESI-MS		79
Pt6	Triphenylphosphine	Pt6(PPh3)4Cl5		ESI-MS		502
Pt6	Glutathione	Pt6(SG)6		ESI-MS		502
Pt8	PAMAM-OH dendrimer	Pt8(C2H2O2S)8		ESI-MS		80
Pt17	Triphenylphosphine	Pt17(CO)12(PPh3)8		ESI-MS, MALDI-MS		503
Pt17	Triphenylphosphine	Pt17(CO)12(PPh3)8		ESI-MS	Cyclic ion mobility, MS/MS (CID)	140
Pt23	2,6-Dimethylphenyl isocyanide	Pt23(XylNC)20(CO)5Cl2		ESI-MS		504
Au2Ni3	Phenylethanethiol	Au2Ni3(SEtPh)8		ESI-MS		505
Ag4Ni2	Dimercaptosuccinic acid	Ag4Ni2(DMSA)4		ESI-MS		506
Au4Cu2	3-Mercaptopropionic acid	Au4Cu2(MPA)5		ESI-MS		507
Au4Ni2	Phenylethanethiol	Au4Ni2(SEtPh)8		ESI-MS		508
Au4Ni2	Phenylethanethiol	Au4Ni2(SEtPh)8		Paper spray MS		509
Au4Pd2	Phenylethanethiol	Au4Pd2(PET)8		ESI-MS		510
Au4Pd2	Phenylethanethiol	Au4Pd2(PET)8		MALDI-MS		511
Au4Pt2	Phenylethanethiol	Au4Pt2(PET)8		MALDI-MS		512
Au3Ag5	Mercaptosuccinic acid	Au3Ag5(MSA)3		ESI-MS		513
Au4Cu4	1,1-Bis(diphenylphosphino)methane, adamantanethiol	[Au4Cu4(Dppm)2(SAdm)5]Br	Br^−	ESI-MS		514
Au6Ag2	2-(Diphenylphosphino)-5-pyridinecarboxaldehyde	[Au6Ag2(C)(L1)6](BF4)4	BF4^−	ESI-MS		515
Au4Ag5	1,1-Bis(diphenylphosphino)methane, adamantanethiol	[Au4Ag5(dppm)2(SAdm)6]^+		ESI-MS		516
Au4Cu5	1,1-Bis(diphenylphosphino)methane, cyclohexanethiol	[Au4Cu5(C6H11S)6(dppm)2](BPh4)	BPh4^−	ESI-MS		514
PdAu8	Triphenylphosphine	PdAu8(PPh3)8		ESI-MS	Ion mobility	517
PdAu9	Triphenylphosphine	PdAu9(PPh3)8(CN)	CN^−	ESI-MS		518
PtAg9	Tris(4-fluorophenyl)phosphine	PtAg9[P(Ph–F)3]7Cl3	Cl^−	ESI-MS		519
Au8Ag3	Triphenylphosphine	Au8Ag3(PPh3)7Cl3	Cl^−	ESI-MS		520
AuCu11	Phenylacetylene, diisopropyldithiophosphate	AuCu11(H){S2P(OiPr)2}6(C≡CPh)3		ESI-MS		521
Ag7Au6	Mercaptosuccinic acid	Ag7Au6(H2MSA)		ESI-MS		522
PtAg12	2,4-Bimethylbenzenethiol, 1,1-bis(diphenylphosphino) methane	PtAg12(dppm)5(SPhMe2)2		ESI-MS		523
Au9M4 (M = Ag, Cu)	Diphenylmethylphosphine	[Au9M4Cl4(PMePh2)8][C2B9H12]·CH2Cl2		ESI-MS		524
CoAu12	1,1-Bis(diphenylphosphino)methane	CoAu12(dppm)6		ESI-MS		525
Ag14−xCux	Fluorothiophenol	Ag14−xCux(SPhF5)12(P(Ph-m-OMe)3)4		ESI-MS		526
PdAg13	Diisopropyldithiophosphate	Pd(H)Ag13(S){S2P(O^iPr)2}10		ESI-MS		527
Ag14M (M = Pd/Pt)	1,3-Bis(diphenylphosphino)propane	([M1Ag14(DPPP)6Cl4](OTf)2	OTf^−	ESI-MS		528
Au7Ag8	1,10-Bis-(diphenylphosphino)ferrocene, proline	Au7Ag8(dppf)3(L-/D-proline)6		ESI-MS		529
CdAu14	tert-Butylthiol	CdAu14(S^tBu)12		ESI-MS		321
Au7Ag9	1,1′-Bis(diphenylphosphino)ferrocene	[Au7Ag9(dppf)3(CF3CO2)7BF4]n	BF4^−	ESI-MS		530
Ag13Cu4	m-Carborane-1,7-dithiol	Ag13Cu4(CBDT)12		ESI-MS		531
AuAg12Cu4	o-Carboranethiol	AuAg12Cu4(o1-CBT)12		ESI-MS		238
Au7Cu10	Adamantanethiol, disphenyl-2-pyridylphosphine	Au7Cu10(1-Adm)3(PPh2Py)6Cl3		ESI-MS		532
Au13Cu4	4-Mercaptobenzoic acid	Au13Cu4(pMBA)12		ESI-MS		533
Au16Ag	Adamantanethiol	[Au16Ag(S-Adm)13]		ESI-MS		534
Pt2Ag15	Adamantanethiol, bis(2-diphenyphosphinophenyl)ether	Pt2Ag15(SAdm)4(DPPOE)4H		ESI-MS		535
Au15Ag3	2,4-Dimethylbenzenethiol	Au15Ag3(SPhMe2)14		ESI-MS		536
Au17M2 (M = Pd, Pt)	Diethylphenylphosphine	M2Au17(depp)10Cl7		ESI-MS		537
AuAg19[Editor37]	O,O-Diisopropyl dithiophosphate	[AuAg19{S2P(O^nPr)2}12]		ESI-MS		538
Au18Cd2	4-Methylbenzenethiol, triphenylphosphine	Au18Cd2(p-MBT)14(PPh3)2		ESI-MS		539
Cu3Ag17	Diisopropyldithiophosphate	Cu3Ag17{S2P(O^nPr)2}12		ESI-MS		540
Au9Ag12	1,1-Bis(diphenylphosphino)methane, adamantanethiol, 4-tert-butylmercaptan	[Au9Ag12(SR)4(dppm)6X6]^3+		ESI-MS		541
Au21−xAgx	tert-Butylthiol	Au21−xAgx(SR)15 (x = 4–8)		ESI-MS		542
Au21−xCux	tert-Butylthiol	Au21−xCux(SR)15 (x = 0–5)		ESI-MS		542
Au16Cu6	tert-Butylphenylacetylene	Au16Cu6(^tBuPhC≡C)18		ESI-MS		543
Au19Cd3	3,5-Dimethylbenzenethiol	Au19Cd3(3,5-DMBT)18		ESI-MS		544
Au22−xCux	tert-Butylphenylacetylene	Au22−xCux(^tBuC6H4C≡C)18		ESI-MS		545
AuAg22	Adamantanethiol	[AuAg22(S-Adm)12]^3+		ESI-MS		546
Au23−xAgx	Adamantanethiol	Au23−xAgx(S-Adm)16		MALDI-MS		547
Au24−xAgx	tert-Butylbenzylmercaptan	Au24−xAgx(TBBM)20		ESI-MS		548
Au25−XAgx	Phenylethanethiol	[Au25−XAgx(PET)18]		ESI-MS		549
Ag5Au20	Captopril	Ag5Au20(Capt)18		ESI-MS		550
Ag6Au19	Triphenylphosphine	[Ag6Au19(MeOPhS)17(PPh3)6]^2+		ESI-MS		551
Ag13Au12	Triphenylphosphine, phenylethanethiol	[Ag13Au12(PPh3)10(SR)5Cl2]^2+		ESI-MS		552
Ag23Pd2	Triphenylphosphine	[Ag23Pd2(PPh3)10Cl7]		ESI-MS		553
Ag23Pt2	Triphenylphosphine	[Pt2Ag23Cl7(PPh3)10]		ESI-MS		554
Ag24Au	1,1-Bis(diphenylphosphino)methane	[AuAg24(dppm)3(SR)17]^2+		ESI-MS		555
Ag24Au	6-Mercaptohexanoic acid	AuAg24(MHA)18		ESI-MS		556
Ag24Au	2,4-Dimethylbenzenethiol	[Ag24Au(DMBT)18]-		ESI-MS		87
Ag24M (M = Pd/Pt)	2,4-Dichlorobenzenethiol	[Ag24M(SR)18](PPh4)2	PPh4^−	ESI-MS		557
Ag24M (M = Pt)	2,4-Dimethylbenzenethiol	[Ag24Pt(DMBT)18]-		ESI-MS	MS/MS (UVPD)	120
Au24M (M = Cd/Hg)	Phenylethanethiol	Au24M(SC2H4Ph)18		ESI-MS, MALDI-MS		86
Au24Pd	3,5-Bis(trifluoromethyl)phenylacetylene	PdAu24(PA)18		ESI-MS		558
Au24Pd	2-Phenylethanethiol	[Au24Pd(PET)18]^−		ESI-MS		559
Au24Pt	tert-Butylbenzenethiol, thiodithiol	[Au24Pt(TBBT)12(TDT)3]		ESI-MS		560
Au24Pt	2-Phenylethanethiol	[Au24Pt(PET)18]^−		MALDI-MS		561
Au24Pt	Alkanethiol	[Au24Pt(SCn)18]^−		ESI-MS	Mass selected PES	207
Au24M (M = Pt, Pd)	3,5-Bis(trifluoromethyl)phenylacetylene	[MAu24(C≡CR)18]^2−		ESI-MS	MS/MS (CID)	562
Au24−xAgxM1 (M = Cd/Hg)	Phenylethanethiol	AgxAu24−xM1(SR)18		ESI-MS		563
Au24−x−yAgxCuyPd	1-Dodecanethiol	Au24−x−yAgxCuyPd(SC12H25)18		MALDI-MS		564
Au25−xCux	2-Phenylethanethiol	[Au25−xCux(PET)18]		MALDI-MS		565
Ag18Cu8	tert-Butylphenylacetylene, 1,3-bis(diphenylphosphino)propane	Ag18Cu8(dppp)4(^tBu-C6H4C≡C)22		ESI-MS		566
Au24Cd2	1-Adamantanethiol, 1,3-bis(diphenylphosphino)propane	Au24Cd2(SAdm)12(dppp)2Cl2	Cl^−	ESI-MS		567
Au25Cd	4-Methylbenzenethiol, triphenylphosphine	Au25Cd(p-MBT)17(PPh3)2		ESI-MS		539
Ag2Au25	Phenylethanethiol	Ag2Au25(SR)18		MALDI-MS		568
Ag15Cu12	Cyclohexanethiol	Ag15Cu12(S-c-C6H11)18(CH3COO)3		ESI-MS		569
Au4Ag23	1,1′-Bis(diphenylphosphino)ferrocene, tert-butylalkynyl	[Au4Ag23(^tBuC≡C)10Cl7(dppf)4]^2+		ESI-MS		570
Au26Pd	2-Phenylethanethiol	Au26Pd(SPh^tBu)20		ESI-MS		346
Au27Cd	1,1′-Bis(diphenylphosphino)ferrocene, adamantanethiol	Au27Cd(SAdm)14(DPPF)Cl	Cl^−	ESI-MS, MALDI-MS		84
Ag16Au13	3-Bromoprop-1-yne, hydroxybenzonitrile	[Au13Ag16(C10H6NO)24]^3−		ESI-MS		571
Ag17Au12	1,3-Benzenedithiol, triphenylphosphine	Au12Ag17(BDT)12(PPh3)4		ESI-MS		572
Ag17Cu12	1,3-Benznedithiol, triphenylphosphine	Ag17Cu12(SR)12(PPh3)4		ESI-MS		573
Ag25Cu4	1,4-Bis(diphenylphosphine)butane, phenylacetylene	Ag25Cu4Cl6(dppb)6(PhC≡C)12		ESI-MS		574
Ag25Cu4	Phenylacetylene, triphenylphosphine	[Ag25Cu4H8Br6(C≡CPh)12(PPh3)12]^3+		ESI-MS		575
Ag28Hg	1,3-Benzenedithiol	Ag28Hg(BDT)12		ESI-MS		576
MAg28 (M = Ni, Pd)	1,3-Benznedithiol, triphenylphosphine	MAg28(BDT)12(PPh3)4		ESI-MS		572
Ag28−XAuxM (M = Ni/Pd/Pt)	1,3-Benzenedithiol, triphenylphosphine	MAuxAg28−X(BDT)12(PPh3)4		MALDI-MS		577
PtAg12Cu12Au4	Adamantanethiol, triphenylphosphine	PtAg12Cu12Au4(S-Adm)18(PPh3)4		ESI-MS		85
Au24Cu6	4-tert-Butylbenzenethiol	Au24Cu6(TBBT)22		ESI-MS		578
Cu28Ag4	Phenylethanethiol, triphenylphosphine	[Ag4Cu28H6(PET)16-Cl8(PPh3)8]		ESI-MS		579
Ag20Cu12	2,4-Dimethylbenzenethiol, 1,1-bis(diphenylphosphino) methane	[Ag20Cu12(SR)14(dppm)6Br8]^2+		ESI-MS		580
Cu20Ag13	Phenylethanethiol, triphenylphosphine	Ag13Cu20(PPh3)4(PET)24]		ESI-MS		581
Au25Cu8	Adamantanethiol, triphenylphosphine	Au25Cu8(S-Adm)19(PPh3)5		MALDI-MS		582
Ag22Cu12	3,5-Bis(trifluoromethyl)phenylacetylene	Ag22Cu12(C≡CR)28		ESI-MS		583
Au34Rh	Polyvinyl-2-pyrrolidone (PVP)	Au34RhCl^−		MALDI-MS		584
Au36−xAgx	tert-Butylbenzenethiol	Au36−xAgx(SPh-^tBu)24		ESI-MS		585
Au38−xAgx	2-Phenylethanethiol	AgxAu38−x(SR)24		MALDI-MS		586
Au36Pd2	2-Phenylethanethiol	Au36Pd2(SC2H4Ph)24		MALDI-MS		400
Ag28Cu12	2,4-Dichlorobenzenethiol	[Ag28Cu12(SR)24]^4−		ESI-MS		587
Ag32Au12	Fluorobenzenethiol	[Ag32Au12(SR)30]^4−		ESI-MS		588
Ag32Cd12	Benzene selenol	[Ag32Cd12(SePh)36]		MALDI-MS		589
Ag32Cu12	Tris(4-methoxyphenyl)phosphine, adamantanethiol	[Ag32Cu12(CH3COO)12(SAdm)12(P(CH3OPh)3)4]		ESI-MS		590
Ag44−xAux	Fluorothiophenol	Ag44−xAux(FTP)26		ESI-MS	MS/MS (CID)	591
Au24+xAg20−x	4-tert-Butylbenzenethiol	Au24+xAg20−x(SPh^tBu)26		ESI-MS		592
Au44−xAgx	4-Trifluoromethylthiophenol	Au44−xAgx(SR)30		ESI-MS		593
Au41Cd6	Phenylmethanethiol	Au41Cd6S2(SCH2Ph)33		ESI-MS		594
Cu47−xAgx	Benzene selenol, triphenylphosphine	[(CuAg)47(PhSe)18(PPh3)6(CF3COO)12H6]		ESI-MS		494
Au19Cu30	3-Ethynylthiophene, ethynylbenzene	[Au19Cu30(C≡CR)22(Ph3P)6Cl2]		ESI-MS		595
Ag20Au12Cu	Pentafluorobenzenethiol	Au12Ag20Cu18(PFBT)36		ESI-MS		596
Ag50−xAux	tert-Butylbenzylmercaptan, 1,1-bis(diphenylphosphino)methane	AuxAg50−x(dppm)6(SR)30		ESI-MS		282
Au12Ag20Cu18	Pentafluorobenzenethiol	Au12Ag20Cu18(PFBT)36		ESI-MS		596
Cu32Au18	4-Methoxythiophenol	[Au18Cu32(SR–O)36]		ESI-MS		597
Ag53−xM	2,4-Dimethylbenzenethiol, 1,3-benzenedithiol	MAg53−x(BDT)12(DMBT)18−y		ESI-MS	MS/MS (CID)	107
Ag42Cu12	3,5-Bis(trifluoromethyl)phenylacetylene	Ag42Cu12(C≡CR)36		ESI-MS		583
Cu56Au	Adamantanethiol	[AuCu56S12(SAdm)20(O3SAdm)12]		MALDI-MS		598
Ag43Au16	2,4-Dichlorobenzenethiol	[Au16Ag43H12(SPhCl2)34]^5−		ESI-MS		599
Au34Ag28	Phenylacetylene	Au34Ag28(PhC≡C)34		ESI-MS		600
Au43Ag38	Dodecanethiol	Au43Ag38(C12H13)36Cl		ESI-MS		601
Au57Ag53	Phenylacetylene	[Au57Ag53(PhC≡C)40Br12]		MALDI-MS		602
Au80Ag30	Phenylacetylene	[Au80Ag30(PhC≡C)42Cl9]Cl		MALDI-MS		603
Au52Cu72	4-Methylthiophenol	Au52Cu72(SPh)55		ESI-MS		604
Au130−xAgx	4-tert-Butylbenzenethiol	Au130−xAgx(SR)55		MALDI-MS		605
Au74Ag60	Phenylacetylene	[Au74Ag60(PhC≡C)40Br12]		MALDI-MS		606
Au137−xMx (M = Ag, Pd)	2-Phenylethanethiol	Au137−xMx(SR)60		ESI-MS		447
Au78Ag66	Phenylacetylene	[Au78Ag66(PhC≡C)48Cl8]		MALDI-MS		606
Au144−xAgx	2-Phenylethanethiol	Au144−xAgx(SR)60		ESI-MS, MALDI-MS		607
Au144−xCux	2-Phenylethanethiol	Au144−xAgx(SR)60		ESI-MS, MALDI-MS		608
Au144−xAgx	Hexanethiol	Au144−xCux(SR)60		ESI-MS, MALDI-MS		609
Au144−xPdx	2-Phenylethanethiol	Au144−xPdx(SR)60		ESI-MS, MALDI-MS		610
Au329−xAgx	2-Phenylethanethiol	Au329−xAgx(SR)84		ESI-MS, MALDI-MS		611

---

Recent advancements in instrumentation have greatly expanded the scope of mass spectrometry. Charge detection MS methods now allow the measurement of charge and mass-to-charge ratio of single ions, facilitating the study of bigger systems such as protein assemblies, viral particles, and nanoparticles, which was previously not possible. Mass photometry, a non-destructive and label-free method for measuring molecular mass in solution, has also emerged as a powerful approach to investigate molecular interactions, including protein and nanocluster binding and aggregation, with high accuracy at the level of single entities. Nano-electro-mechanical sensor-based MS (NEMS-MS), which directly measures the inertial mass of particles without relying on charge states, represents a powerful emerging approach for materials research. Its nanoscale dimensions provide exceptional miniaturisation potential, making it attractive for the characterisation of nanoclusters and heterogeneous materials at the single-particle level.²¹

While this review focused on characterizing ions, they can also serve as precursors for creating materials that lead to various applications. The examples presented in Section 7 also point to an “ionic path” for cluster-based materials. The application of mass spectrometry has tremendously expanded from mass analysis to materials processing. Soft ionisation and deposition methods such as electrospray ionisation, electrospray deposition, and soft landing make it possible to transfer intact molecular ions or clusters onto substrates under gentle conditions. These techniques enable the assembly of thin films and nanostructures with controlled properties, which can be useful in sensing, catalysis, and nanoelectronics. Given that these methods operate under mild and tunable conditions, they are particularly suitable for preserving fragile systems during their synthesis and characterisation. The electrospray-deposited clusters and cluster superstructures could be characterised using cryogenic electron microscopy (cryo-EM) and microcrystal electron diffraction (microED). These advances could integrate MS with structural techniques, opening a new dimension in this area.

The progress in ion activation and spectroscopic methods has further improved the structural analysis of nanoclusters. Advanced techniques such as ion mobility spectrometry, tandem mass spectrometry, and ultraviolet photodissociation allow the elucidation of isomeric structures, dissociation pathways, and core–shell structure arrangements. Advancements in multidimensional MS, particularly two-dimensional tandem MS, enable the rapid and high-throughput screening of complex mixtures, and these inputs can be extended to other systems to accelerate the discovery and optimisation of nanoclusters, alloys, and hybrid materials.²⁰² Laser-based action spectroscopy,²⁰³ when used along with ion mobility, enables the study of excited states and weak intermolecular interactions. Recent developments, such as cyclic ion mobility, allow recirculation of ions for enhanced resolution, making it possible to distinguish nearly identical species.²⁰⁴

Future developments in this field lie in the integration of mass spectrometry with other complementary characterisation techniques. Approaches that combine MS with electron microscopy,²⁰⁵ infrared, Raman,²⁰⁶ UV–vis and photoelectron spectroscopy,²⁰⁷etc. could derive correlations among composition, morphology, structure, and electronic properties. These multifaceted approaches could unveil the relationship between structure and functions in nanoscale materials. Ultrahigh-resolution mass spectrometry imaging, widely applied for mapping biomolecules in biological samples,^208,209 can be extended to materials research to probe the dopants, interfaces, and nanoscale defects in heterogeneous solids with molecular precision. Native-state approaches, such as matrix-landing MS,²¹⁰ expand the scope of intact nanoclusters or supramolecular assemblies to be transferred directly from the gas phase onto surfaces for electron microscopy imaging or device integration.

In parallel, theoretical and computational approaches are also advancing rapidly. Machine-learned interatomic potentials, such as the Atomic Cluster Expansion (ACE) model developed by McCandler et al., are enabling long-timescale molecular dynamics simulations with near-DFT (density functional theory) accuracy and much greater efficiency. These models offer valuable insights into ligand exchange, reactive isomerism, and structural rearrangements in nanoclusters, which align with experimental observations. A growing direction in this field is the integration of mass spectrometry with theoretical modelling, where MS data are combined with DFT and other computational methods to predict stable geometries, electronic structures, and fragmentation pathways. The combination of experiment and simulation could provide a better understanding of the gas-phase chemistry and aggregation-induced properties of nanoclusters.²¹¹ Finally, incorporating MS into closed-loop smart synthesis frameworks driven by artificial intelligence and automation, will enable real-time feedback between synthesis and property assessment, thereby accelerating the rational design of materials with tailored catalytic, optical, and electronic properties.²¹² The integration of real-time MS analysis with computational modelling and machine learning will enable the design of clusters with targeted composition, stability, and functionality, transforming MS into a predictive tool for materials discovery.

To conclude, the scope of mass spectrometry has significantly expanded from an analytical tool. Currently, it occupies a central position across various disciplines, including materials science, nanotechnology, and biochemistry. With its broad capabilities, ranging from synthesis and soft landing to high-resolution structural studies and integration with computation, it redefines the design and investigation of materials at the atomic scale. Continued advancements in the field of mass spectrometry will establish it as a foundational tool for developing next-generation functional nanomaterials.

Author contributions

T. P. conceived the idea and initiated the project. A. J. drafted the manuscript and prepared the figures. B. S. S. compiled the list of clusters. All authors reviewed and approved the final version of the manuscript.

Conflicts of interest

There are no conflicts to declare.

Data availability

All the data supporting this review article have been included in the main article itself.

Acknowledgements

A. J. acknowledges the MHRD for the PMRF grant. B. S. S. thanks the Council of Scientific & Industrial Research (CSIR) for the Shyama Prasad Mukherjee (SPM) research fellowship. T. P. thanks the SERB, India, for funding through the research grant, SPR/2021/000439, and through the JC Bose Fellowship. T. P. also acknowledges funding from the Centre of Excellence (CoE) on Molecular Materials and Functions through the Institute of Eminence Scheme, IIT Madras.

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