Themed collection 2021 Frontier and Perspective articles
State of the art developments and prospects of metal–organic frameworks for energy applications
The state of the art developments and future prospects of MOFs and their energy-based applications are summarized.
Recent advances in externally controlled ring-opening polymerisations
Switchable catalysis is a powerful tool in the polymer chemist's toolbox as it allows on demand access to a variety of polymer architectures.
Reductively disilylated N-heterocycles as versatile organosilicon reagents
The reductively disilylated N-heterocyclic systems diligently give up electrons thereby demonstrating as versatile reagents in the salt-free reduction of transition metals, main-group halides, in organic transformations and in materials syntheses.
Phosphorescent NIR emitters for biomedicine: applications, advances and challenges
This review describes the current state of the art in the chemistry of phosphorescent NIR emitters with a particular focus on their application in biomedicine as luminescent probes, sensors and theranostic agents.
Transmetalation of boronic acids and their derivatives: mechanistic elucidation and relevance to catalysis
The Suzuki–Miyaura reaction (the cross-coupling reaction of boronic acids with organic halides catalysed by Pd complexes) has been recognised as a useful synthetic organic reaction that forms a C(sp2)–C(sp2) bond.
A review on two-dimensional (2D) perovskite material-based solar cells to enhance the power conversion efficiency
With perovskite materials, rapid progress in power conversion efficiency (PCE) to reach 25% has gained a significant amount of attention from the solar cell industry.
Impact of the coordination of multiple Lewis acid functions on the electronic structure and vn configuration of a metal center
The number of electrons that a metal center provides to the bonding orbitals for coordination of multiple π-acceptor ligands is not a direct function of the number of ligands, and consideration must be given to the availability of metal orbitals.
In defence of oxidation states
In this Perspective, some of the criticisms which have been made concerning the use of oxidation states are addressed, particularly in the context of the teaching of inorganic chemistry.
A complementary characterisation technique for spin crossover materials; the application of X-ray photoelectron spectroscopy for future device applications
X-ray Photoelectron Spectroscopy (XPS) has emerged as a complementary technique for the analysis of spin-crossover in the surface layers of a material.
Area selective deposition using alternate deposition and etch super-cycle strategies
Area selective deposition by super-cycle alternating atomic layer deposition and etch-back processes.
Kinetics of Cu(II) complexation by ATCUN/NTS and related peptides: a gold mine of novel ideas for copper biology
The aim of this perspective is to help revive studies of the kinetics of formation and exchange in Cu(II)–peptide complexes. Such studies have the power to reveal novel reactive intermediates and set timeframes for actual physiological processes.
Progress of metal nanoclusters in nucleic acid detection
Metal nanoclusters (MNCs), including Ag NCs, Cu NCs, and Au NCs, can be used as fluorescent probes for nucleic acid testing. Identification of DNA fragments and trace detection of miRNA (LOD as low as aM) can be achieved.
Concanavalin A: coordination diversity to xenobiotic metal ions and biological consequences
Regulation of metal coordination in ConA induces its structural conformation and biological functions.
Acid and base strength variations: rationalization for cyclic amine bases and acidic aqua cations
Recent experimental and theoretical results for the title compounds are critically examined by means of interlinked thermodynamic cycles and observed trends in acid and base strength rationalized by using changes in simple chemical concepts.
The diverse functions of isocyanides in phosphorescent metal complexes
This Perspective describes the diverse roles played by isocyanides in supporting photoluminescent transition metal complexes.
Post-synthetically modified metal–organic frameworks for sensing and capture of water pollutants
Contextualising the discovery of metal–organic frameworks for selective sensing and capture of water pollutants, advances in their post-synthetic design approaches are reviewed.
Deoxygenative hydroboration of carboxamides: a versatile and selective synthetic approach to amines
This perspective overviews the developments in deoxygenative hydroboration of carboxamides, focusing on mechanistic aspects of these transformations and advantages of the hydroboration approach over hydrogenation and hydrosilylation reactions.
Alkali /alkaline earth-based metal–organic frameworks for biomedical applications
This review mainly introduces the application of A/A-E MOF materials in drug delivery, sensing, and some materials with unique biomedical applications, and elaborates the challenges, obstacles and developments in future.
Cancer molecular biology and strategies for the design of cytotoxic gold(I) and gold(III) complexes: a tutorial review
A perspective on the development of gold(I/III) anticancer agents is given, covering the core concepts of apoptosis in cancer cell biology and macromolecular drug targets. Design elements that elicit cytotoxicity and stability are highlighted.
Bioinspired mononuclear Mn complexes for O2 activation and biologically relevant reactions
An interest in harnessing the oxidizing power of O2 has led to the synthetic models of Mn-dependent enzyme active sites. Here, we describe the recent advancements to the development of bioinspired mononuclear Mn complexes for O2 activation.
Recent advances in graphitic carbon nitride as a catalyst for heterogeneous Fenton-like reactions
g-C3N4 based materials exhibit considerable potential in Fenton-like reactions. The g-C3N4 material helps to enlarge the surface area and to provide more available active sites. g-C3N4 is involved in charge transfer. g-C3N4 is engaged as a suitable platform.
Pincer-supported metal/main-group bonds as platforms for cooperative transformations
Constraining metal/main-group bonds within a pincer framework has allowed the elucidation of new and powerful modes of cooperative reactivity. This Perspective highlights recent findings and areas for further development.
Carbenes and phosphonium ylides: a fruitful association in coordination chemistry
The essential role of carbon as coordinating element is evidenced here through the different associations involving carbene and phosphonium ylide ligands.
Intramolecular attack on coordinated nitriles: metallacycle intermediates in catalytic hydration and beyond
Intramolecular S-OH or P-OH attack on a coordinated nitrile yields a metallacycle in the proposed mechanism of nitrile hydratase and related synthetic catalysts.
Hetero-tri-spin systems: an alternative stairway to the single molecule magnet heaven?
Three different spin carriers inside the same molecular system is a promising strategy towards multi-functional magnetic materials. The possible spin topologies have been reviewed and analysed to identify the most promising one.
The rich physics of A-site-ordered quadruple perovskite manganites AMn7O12
Research results on A-site-ordered quadruple perovskite manganites AMn7O12 are reviewed and unresolved problems and future directions are highlighted.
Recent advances in molecular logic gate chemosensors based on luminescent metal organic frameworks
This review covers the latest advancements of molecular logic gates based on LMOF. The classification, design strategies, related sensing mechanisms, future developments, and challenges of LMOFs-based logic gates are discussed.
Supramolecular catalysis: the role of H-bonding interactions in substrate orientation and activation
This perspective highlights the importance of hydrogen bonds in supramolecular complexes for the recognition and binding of a substrate that subsequently influence and/or control the catalytic outcome.
Enzyme-activated probes in optical imaging: a focus on atherosclerosis
This perspective provides an overview of the design requirements and fluorogenic mechanisms of enzyme-activatable probes in optical imaging, focusing particularly on detecting enzymatic targets overexpressed in vulnerable atherosclerotic plaque.
Flexible luminescent non-lanthanide metal–organic frameworks as small molecules sensors
Non-lanthanide metal–organic frameworks with flexible structure and luminescence properties are systematically discussed as potential small molecule sensors.
Metal complexes against breast cancer stem cells
With the highest incidence, breast cancer is the leading cause of cancer deaths among women in the world.
TEMPO-radical-bearing metal–organic frameworks and covalent organic frameworks for catalytic applications
This perspective article focuses on TEMPO-bearing MOFs and COFs for use in catalytic applications.
Current advances in bio-fabricated quantum dots emphasising the study of mechanisms to diversify their catalytic and biomedical applications
Recent progress in the bio-mediated preparation of quantum dots as a greener and efficacious approach towards their surface functionalization in light of their varied applications is summarised.
The chemistry of dithietes, 1,2,5,6-tetrathiocins and higher oligomers
The chemistry of 1,2-dithietes is compared with 1,2,5,6-tetrathiocins and higher oligomers, providing access to a diversity of sulfur-rich heterocycles and dithiolate complexes.
Two-dimensional materials as solid-state nanopores for chemical sensing
The advances of 2D materials such as graphene, MoS2 and 2D MOF nanosheets as solid-state nanopores for analyzing biomolecules are discussed.
Advancing the extended roles of 3D transition metal based heterostructures with copious active sites for electrocatalytic water splitting
This review highlights the importance of 3D transition metal based heterostructures with improved active sites for metal hydroxides, LDHs, oxides, sulfides and metal phosphides and the influencing roles of 3D foams in water splitting.
Diorganyl diselenides: a powerful tool for the construction of selenium containing scaffolds
Organoselenium compounds find versatile applications in organic synthesis, materials synthesis, and ligand chemistry.
Insights into the past and future of Janus-di-N-heterocyclic carbenes
Insights into the past and future of Janus-head di-NHC ligands.
Influence of the choice of precursors on the synthesis of two-dimensional transition metal dichalcogenides
This perspective illustrates the recent conceptual advancements in the growth of layered vdW TMDCs using either multi-source precursors or single-source precursors and provides a critical evaluation of these two approaches.
A review on platinum(0) nanocatalysts for hydrogen generation from the hydrolysis of ammonia borane
This review reports a survey on the progress in developing highly efficient platinum nanocatalysts for the hydrolytic dehydrogenation of ammonia borane (AB).
Molecular copper iodide clusters: a distinguishing family of mechanochromic luminescent compounds
This perspective describes the survey of the family of mechanochromic luminescent cubane copper iodide clusters. Studies of their mechanochromic luminescence properties are presented along with investigations to elucidate the underlying mechanism.
Designed polynuclear lanthanide complexes for quantum information processing
The design of dissymmetric organic ligands has been exploited to produce heterometallic dinuclear and trinuclear lanthanide-based coordination compounds with the requirements to act as logical quantum gates for spin-based quantum computing.
Fluorescent chemosensors containing redox-active ferrocene: a review
The analytical novelty and sensing mechanisms of some important ferrocene based fluorescent chemosensors are discussed to open new scopes for future research.
Dehydrohalogenation reactions in second-sphere coordination complexes
An overview on the latest advances in dehydrohalogenation and hydrohalogenation reactions in the solid-state involving hydrogen bonded outer sphere halometallates salts is reported.
Recent progress on pristine two-dimensional metal–organic frameworks as active components in supercapacitors
Recent progress on 2D conductive MOFs and 2D layered MOFs containing pillar-layered MOFs and 2D nanosheets as electrode materials in SCs is reviewed, including synthetic design strategies, electrochemical performances, and working mechanisms.
Exploring the structure–property schemes in anion–π systems of d-block metalates
The emerging picturesque landscape of anion–π systems involving d-block metalates (cyanidometalates, halogenometalates, polyoxometalates) is presented based on a literature review and the personal research experience of the authors.
Metal–organic frameworks as proton conductors: strategies for improved proton conductivity
Various innovative strategies and methodologies for the development of MOFs and coordination polymers based materials for high performance solid state proton conductors and proton exchange membranes are outlined.
N-Heterocyclic silylenes in coinage metal chemistry: an account of recent advances
This review summarizes the recent developments in the field of silylene–coinage metal chemistry.
Trends in computational molecular catalyst design
This perspective article summarizes current computational approaches used in molecular catalyst design, highlights their main advantages and limitations as well as the opportunities for automation and advanced machine learning algorithms.
Hybrid dual-function thermal energy harvesting and storage technologies: towards self-chargeable flexible/wearable devices
This review focuses on the advances in thermally-chargeable supercapacitors for flexible/wearable applications, starting from an overview of thermoelectric generators and supercapacitors up to the rational design of all-in-one hybrid technologies.
A review on metal–organic framework-derived anode materials for potassium-ion batteries
Research progress of MOF-derived anode materials for potassium ion batteries has been presented based on different organic ligands.
New frontiers: 1,4-diphosphinines and P-bridged bis(NHCs)
This review describes synthetic concepts and breakthroughs in 1,4-diphosphinine and related P-bridged bis(NHCs). Starting from monocyclic 1,4-dihydro-1,4-diphosphinines the most promising achievements of tricyclic 1,4-diphosphinines and related bis(NHCs) are covered.
New avenues for mechanochemistry in zeolite science
Recent advances of mechanochemical methods in the field of zeolite science are reviewed and their future potential highlighted.
Organoselenium ligands for heterogeneous and nanocatalytic systems: development and applications
Organoselenium ligands have attracted great attention among researchers during the past two decades.
Organo-functionalized polyoxovanadates: crystal architecture and property aspects
The latest progress on polyoxovanadates modified with organic ligands or transition metals and organic ligands is summarized. Not only the structural features and main applications but also the challenges and the focus of future research on POV-based materials are discussed.
Bismuth species in the coordination sphere of transition metals: synthesis, bonding, coordination chemistry, and reactivity of molecular complexes
Bismuth species in the coordination sphere of transition metals show widely tunable bonding situations, impacting their stoichiometric and catalytic reactivity.
Recent progress in the development of MOF-based optical sensors for Fe3+
A summary of Fe3+ detection by luminescent MOFs and their mechanistic approaches are highlighted in this article based on recent publications.
Recent advances in organophosphorus–chalcogen and organophosphorus–pincer based macrocyclic compounds and their metal complexes
This short review describes the recent developments in organophosphorus–chalcogen and organophosphorus–pincer macrocycles and their metal complexes with emphasis on synthetic methodologies.
Liquid atomic layer deposition as emergent technology for the fabrication of thin films
Liquid atomic layer deposition (LALD) has emerged as a complementary technology of atomic layer deposition (ALD) to help overcome some of the challenges currently faced from working in the gas-phase.
Keep it tight: a crucial role of bridging phosphine ligands in the design and optical properties of multinuclear coinage metal complexes
Stereochemical properties and flexibility of organic spacer in oligodentate phosphine ligand and spatial separation of phosphorus atoms one relative to other regulate the composition and architecture of multinuclear compounds of coinage metals.
Coordination sphere hydrogen bonding as a structural element in metal–organic Frameworks
Coordination sphere hydrogen bonding in coordination polymers and metal–organic frameworks (MOFs) is examined as a structurally and chemically stabilising influence, accessible through ligand design strategies.
Indium metal–organic frameworks based on pyridylcarboxylate ligands and their potential applications
This review focuses on the recent developments in the field of In-MOFs constructed from pyridylcarboxylate ligands, including their synthesis, crystal structures, stability and potential applications.
Structural insights into the recognition of DNA defects by small molecules
In this review, we have underlined the application of transition metal chemistry in biological systems.
Ion-conductive metal–organic frameworks
This perspective provides an overview of ion-conductive metal–organic frameworks with various ionic carriers, such as protons, hydroxide ions, lithium ions and other ions.
Constructing chiral polyoxometalate assemblies via supramolecular approaches
Chirality generation, induced chirality transfer, and the functionalization of polyoxometalate-based complexes and their self-assembly constructed through supramolecular approach are systematically reviewed.
Spin crossover phenomena in long chain alkylated complexes
This review presents a discussion of soft metal complexes with a focus on spin crossover behaviours that are associated with structural phase transition, including liquid crystal LC transition.
Metal–organic frameworks with the gyroid surface: structures and applications
This review article summarizes the assembly, structures, and topologies of gyroidal metal–organic frameworks. Their applications in gas adsorption, catalysis, sensors, and luminescent materials are also discussed in detail.
A review of the recent progress on heterogeneous catalysts for Knoevenagel condensation
One of the most crucial attributes of synthetic organic chemistry is to design organic reactions under the facets of green chemistry for the sustainable production of chemicals.
Control of guest binding behavior of metal-containing host molecules by ligand exchange
Structural transformation driven by ligand exchange was effectively utilized to control the host–guest binding behavior of metal-containing host molecules.
Recent advances in Cu2O-based composites for photocatalysis: a review
This review summarizes the crystal structures, modification methods, application prospects, and electron transfer mechanisms of different Cu2O-based photocatalysts.
About this collection
This web collection contains the Frontier and Perspective articles published in Dalton Transactions in 2021.