Low-coordinate first-row transition metal complexes in catalysis and small molecule activation
In this Perspective, we will highlight selected examples of transition metal complexes with low coordination numbers whose high reactivity has been exploited in catalysis and the activation of small molecules featuring strong bonds (N2, CO2, and CO).
2,2′-Dipyridylamines: more than just sister members of the bipyridine family. Applications and achievements in homogeneous catalysis and photoluminescent materials
2,2′-Dipyridylamine derivatives: Discreet members of the polydentate nitrogen ligand familly with underestimated potential.
Water exchange in lanthanide complexes for MRI applications. Lessons learned over the last 25 years
Coordination chemistry offers convenient strategies to modulate the exchange of coordinated water molecules in lanthanide-based contrast agents.
Group 11 tris(pyrazolyl)methane complexes: structural features and catalytic applications
Tris(pyrazolyl)methane ligands (Tpmx) have been for years a step behind their highly popular boron-anionic analogues, the tris(pyrazolyl)borate ligands (Tpx).
Direct conversion of methane to methanol with zeolites: towards understanding the role of extra-framework d-block metal and zeolite framework type
This Perspective article highlights the latest advances in the field of direct methane to methanol conversion by zeolites containing first row, extra-framework d-block metals (Mn, Fe, Co, Ni, Cu and Zn).
Transition metal catalysed direct selanylation of arenes and heteroarenes
Recent outstanding advances in the C–Se bond formation through transition metalcatalysed direct selanylation, providing new insights into their mechanistic aspects, were provided in this perspective.
Recent developments in single-molecule toroics
An update overview of emerging single-molecule toroics (SMTs) is expounded to elucidate the strategy to design SMTs and ultimately inspire the seeking of SMTs with enhanced toroidal moment.
Superparamagnetic iron oxide nanoparticulate system: synthesis, targeting, drug delivery and therapy in cancer
Usefulness of Superparamagnetic Iron oxide Nanoparticulate system for biomedical applications through targeting, drug delivery and therapy.
Perovskites with d-block metals for solar energy applications
In this review, we present the most characteristic photoactive perovskites that can be formed with the help of d-block metals.
Structure and reactivity of the first-row d-block metal-superoxo complexes
This review discusses the structure and reactivity of metal-superoxo complexes covering all ten first-row d-block metals from Sc to Zn.
A look at periodic trends in d-block molecular electrocatalysts for CO2 reduction
Periodic trends in the electronic structure of the transition metal centers can be used to explain the observed CO2 reduction activities in molecular electrocatalysts for CO2 reductions. Research activities concerning both horizontal and vertical trends have been summarized with mononuclear complexes from Group 6 to Group 10.
Fe in biosynthesis, translocation, and signal transduction of NO: toward bioinorganic engineering of dinitrosyl iron complexes into NO-delivery scaffolds for tissue engineering
The ubiquitous physiology of nitric oxide enables the bioinorganic engineering of [Fe(NO)2]-containing and NO-delivery scaffolds for tissue engineering.
Evolution and understanding of the d-block elements in the periodic table
The d-block elements have played a critical role in the development of the modern periodic table.
The past, present, and future in the nomenclature and structure representation of inorganic compounds
Where we have been and where we are going in precisely describing structures of inorganic compounds.
The Chatt reaction: conventional routes to homoleptic arenemetalates of d-block elements
Homoleptic arenemetalates, including the depicted [K(18-crown-6)]2[Hf(C14H10)3], are often useful sources of “naked” metal anions and have been obtained for several transition metals via the Chatt reaction, named in honor of Joseph Chatt, a giant of chemistry.
The chemistry of guanidinate complexes of the platinum group metals
In the present Perspective article, synthetic and structural aspects, reactivity studies and applications of platinum group metal complexes containing guanidinate ligands are discussed.
Chelate rings of different sizes with non-innocent ligands
Redox-active unsaturated chelate ligands can be realised with different ring sizes of the resulting metallacycles.
Ethylene polymerization of nickel catalysts with α-diimine ligands: factors controlling the structure of active species and polymer properties
In the present perspective, the recent advances of α-diimine nickel based catalysts of ethylene polymerization, focusing on the relationships between catalyst structures and their catalytic properties are discussed.
Chemistry and applications of cyanoximes and their metal complexes
During the past three decades, considerable research effort has been dedicated to a new class of organic ligands – cyanoximes – which have the general formula NC–C(NOH)-R, where R is an electron-withdrawing group. In total, 44 different cyanoximes were prepared and characterized thus far.
Phosphorus dendrimers functionalised with nitrogen ligands, for catalysis and biology
Phosphorus dendrimers (dendrimers having one phosphorus atom at each branching point) possess versatile properties, depending on the type of their terminal functions.
Small-molecule activation with iron porphyrins using electrons, photons and protons: some recent advances and future strategies
Substituted tetraphenyl Fe porphyrins are versatile molecular catalysts for the activation of small molecules (such as O2, H+ or CO2), which could lead to renewable energy storage, the direct production of fuels or new catalytic relevant processes.
Recent advances in bioinspired proton-coupled electron transfer
Fundamental aspects of PCET continue to attract attention. Understanding this reaction type is desirable for small-molecule activation and solar energy conversion.
On the preferences of five-membered chelate rings in coordination chemistry: insights from the Cambridge Structural Database and theoretical calculations
We illustrate, combining experimental and theoretical results, that the five-membered chelate ring is able to adapt itself to a great variety of metal ions.
Synthesis of organometallic pentalenide complexes
Challenges and opportunities in the synthesis of pentalenide complexes are reviewed from a practical point of view.
Cu(I)–O2 oxidation reactions in a fluorinated all-O-donor ligand environment
This perspective highlights the effects of O-donor fluorinated ligands on Cu–O2 chemistry, with intermediates capable of substrate oxidation reactivity.
Telluraporphyrinoids: an interesting class of core-modified porphyrinoids
This perspective presents a concise overview of the developments in telluraporphyrinoid chemistry since its inception.
End-functional polyolefins for block copolymer synthesis
Block copolymers containing polyolefin (red) and polar (blue) segments may be synthesised via end-functionalised polyolefins from metal-catalysed routes.
Ferrocene-appended pharmacophores: an exciting approach for modulating the biological potential of organic scaffolds
The present review article describes the recent developments (2014–18) on the synthesis of ferrocene-based pharmacophores with the specific benefits of introducing/replacing organic pharmacophores with the ferrocene core for desired bioactivities.
Emerging platinum(IV) prodrugs to combat cisplatin resistance: from isolated cancer cells to tumor microenvironment
In this Perspective, we discuss various types of novel cisplatin-based Pt(IV) complexes including those targeting the tumor microenvironment.
In pursuit of advanced materials from single-source precursors based on metal carbonyls
In this perspective, the development of single-source precursors and their relative advantages over multiple source approaches for the synthesis of metal pnictide solid state materials is explored.
Pandora's box of binary tungsten iodides
More than 20 binary tungsten iodides have been discovered. This was possible due to a new synthesis of W3I12 through halide exchange reaction and by thermal scanning. Depending on the I2 partial pressure compounds can incorporate or release I2. On heating they undergo self-reduction. Some tungsten iodide clusters can be directly transferred into solution.
Modulation of the reactivity of nitrogen mustards by metal complexation: approaches to modify their therapeutic properties
Metal complexation of nitrogen mustards shows promise with an ability to control the mustards’ reactivity, perform selective hypoxia activation, overcome resistance, and control GSH deactivation.
Kinetics and mechanisms of catalytic water oxidation
This review discusses the kinetics and mechanisms of chemical, electrocatalytic and photocatalytic water oxidation by homogeneous and heterogeneous transition metal catalysts.
Heterometallic grids: synthetic strategies and recent advances
This article reviews the most up-to-date progress in heterometallic grid-like complexes and highlights the recent work in 3d–4f heterometallic grids, aiming at a better understanding of the self-assembly and magnetic properties of heterometallic grids.
Near-infrared photothermally activated nanomachines for cancer theragnosis
Near-infrared photothermal-activated nanoagents: a promising platform for accurate diagnosis and efficient cancer eradication.
Water-soluble metal nanoclusters: recent advances in molecular-level exploration and biomedical applications
Recent advances of water-soluble metal nanoclusters (MNCs) in designing highly luminescent MNCs, ligand shell engineering, tracking MNC's growth processes, and biomedical applications are highlighted.
A critical perspective on rechargeable Al-ion battery technology
Efforts should be devoted to lowering the cost of Al-ion batteries, specifically those of electrolytes and current collectors.
The surface chemistry of metal–organic frameworks and their applications
Recent highlights in the surface modification of metal–organic frameworks, from new functionalization protocols to visualisation and application, are discussed.
Multiple activations of CH bonds in arenes and heteroarenes
Re2(CO)8(μ-C6H5)(μ-H) reacts with anthracene four times to yield the quadruply CH activated complex [Re2(CO)8(μ-H)]4(μ-η2-1,2-μ-η2-3,4-μ-η2-5,6-μ-η2-7,8-C14H6).
New frontiers for solid-state NMR across the periodic table: a snapshot of modern techniques and instrumentation
Advances in solid-state NMR spectroscopy which continue to open up the periodic table to further exploration are surveyed.
Nucleophilic substitution: a facile strategy for selective B–H functionalization of carboranes
Nucleophilic substitution of cage BH serves as a brand new strategy for straightforward and regioselective cage B–H functionalization of carboranes.
Emerging chemical tools and techniques for tracking biological manganese
This frontier article discusses chemical tools and techniques for tracking and imaging Mn ions in biology.
Recent advances in self-assembled amidinium and guanidinium frameworks
Recent advances in amidinium and guanidinium-containing hydrogen-bonded framework materials are highlighted.
Near-infrared-emissive metal–organic frameworks
We describe the recent progress in near-infrared-emissive metal–organic frameworks, and especially highlight their appealing applications in bio-imaging, sensing and barcoding.
Size, shape and interface control in gold nanoparticle-based plasmonic photocatalysts for solar-to-chemical transformations
The activity of gold nanoparticle-based plasmonic photocatalysts can be enhanced through the ingenious control of the size, shape and interface.
Coordination-induced structural changes of DNA-based optical and electrochemical sensors for metal ions detection
This article highlights the coordination-induced structural changes of DNA-based optical, electrochemical and optical–electrochemical-combined sensors for metal ions detection.
From corannulene to larger carbon bowls: are they better for multiple metal encapsulation?
The effects of size, charge and symmetry of carbon π-bowls on their supramolecular assembly and metal ion intercalation trends are discussed.
Metal nanoparticles embedded in AIEE active supramolecular assemblies: robust, green and reusable nanocatalysts
Multi-functional AIEE-active supramolecular assemblies act as nanoreactors for the preparation of different types of metal NPs. The in situ generated metal NPs stabilized by supramolecular assemblies act as nanocatalysts for various organic transformations under thermal/visible light irradiation.
Heavier pnictogens – treasures for optical electronic and reactivity tuning
We highlight recent advances in organopnictogen chemistry contrasting the properties of lighter and heavier pnictogens.
On the activation of hypercoordinate iodine(III) compounds for reactions of current interest
Mechanistic insights into different modes of activation of hypercoordinate iodine(III) compounds.
Real-time monitoring of electrochemical reactions on single nanoparticles by dark-field and Raman microscopy
Dark-field and Raman microscopy to probe the single NP electrochemistry in real time.
Copper hydride clusters in energy storage and conversion
Copper hydride clusters of variable nuclearity are derived from hydrogen and HCOOH as emerging energy storage materials and models.
Flux crystal growth: a versatile technique to reveal the crystal chemistry of complex uranium oxides
Molten flux crystal growth is a thriving field for the discovery of uranium oxides.
Recent advances in single molecule magnetism of dysprosium-metallofullerenes
Encapsulation of dysprosium ions in fullerenes results in efficient air stable single molecule magnets, which can be used in preparation of various 1D, 2D, and 3D assemblies.
Post-synthetic diamine-functionalization of MOF-74 type frameworks for effective carbon dioxide separation
Post-synthetic methods are considered facile and effective for adjusting a material's properties. This frontiers article highlights recent advances in the post-synthetic modifications of MOF-74 type frameworks, whose high-density exposed metal sites are grafted by various diamines, leading to the tuning of CO2 adsorption capabilities.
Materials for electrochemical ammonia synthesis
Direct electrochemical synthesis of ammonia is proposed as a means of reducing the carbon footprint of the fertiliser industry, as well as providing new opportunities for carbon-free liquid energy storage.
Recent developments in the chemistry of metal oxopolyazides
The recent acomplished syntheses of novel metal oxopolyazides VO(N3)3, NbO(N3)3, NbO(N3)3·2CH3CN, MoO(N3)3, MoO(N3)3·2CH3CN, WO(N3)4, WO(N3)4·CH3CN, MoO2(N3)2, MoO2(N3)2·2CH3CN, WO2(N3)2, WO2(N3)2·2CH3CN and UO2(N3)2·CH3CN by the author is reviewed.
A revolution of photovoltaics: persistent electricity generation beyond solar irradiation
The integration utilization of solar energy and waste energies by photovoltaics is regarded as a promising solution to resolve energy crisis and environmental pollution problems.
Schiff-base macrocyclic ZnII complexes based upon flexible pendant-armed extended dialdehydes
This Frontier article reviews Schiff-base ZnII macrocycles derived from flexible pendant-armed extended dialdehydes including structure-determining factors in template-directed syntheses, further post-modifications and applications.
Defect engineering on electrocatalysts for gas-evolving reactions
This review focuses on the recent advance in defect engineering of electro-catalysts for specific electro-catalytic applications.
About this collection
This web collection contains the Frontier and Perspective articles published in Dalton Transactions in 2019.