Themed collection 2018 Frontier and Perspective articles

Here we summarize recent progress in the design and application of innovative osmium compounds as anticancer agents with diverse modes of action, as organelle-targeted imaging probes and photosensitizers for photodynamic therapy.

The current synergistic effect and mechanism between LDHs and other flame retardant additives for polymers are summarized.

In this new hypothesis, we propose a complete catalytic cycle involving a charge-rearrangement-induced Mn^VII–dioxo species on the dangling Mn4 during the S₃ → S₄ transition. The O–O bond is formed within this Mn^VII–dioxo site.

The state-of-the-art of metallorganic-based molecular rectification is reviewed with an emphasis on asymmetric five-coordinate Fe^III-containing surfactants in electrode|LB film|electrode assemblies.

Recent accomplishments in the syntheses of Au nanoparticles and nanocluster supported on carbon materials and applications to electroxidation are reviewed.

This Perspective highlights relationships between chemical features of metal bis(acetylide) complexes and their electrical response in a molecular junction.

Teaching inorganic chemistry using the primary literature motivates students to learn deeply and to engage with the important discoveries of the field.

Recent advances (2015–) in the catalytic conversion of CO₂ by metal-based and metal-free systems are discussed.

This perspective paper highlights the insights obtained through experimental and computational probes of magnetic metal–organic frameworks at the atomic scale.

By mostly focusing on the findings of our group, this concise review provides insights into the development of promising new host–guest optical materials based on sol–gel assemblies of versatile hosts and highly luminescent guests.

This Perspective compares the chemistries of s-block metal complexes of isoelectronic PC(H)P- and PNP-bridged, chalcogen-centred monoanions with a focus on the unique behavior of the C(H)-bridged systems.

The transformative character of the reported 3d–4f Coordination Clusters (CCs) in catalytic reactions is summarised, demonstrating the potential of this emerging field.

From conventional synthesis to green transformations: a brief literature overview and insight for the synthesis of Ag nanoparticles.

This paper describes our recent progress in catalytic nitrogen fixation using transition metal–dinitrogen complexes as catalysts.

This Perspective describes the mechanism-based development of iron-group catalysts for the asymmetric hydrogenation of ketones and imines.

Herein, we highlight relevant π-systems based on six-membered phosphorus heterocycles as well as their potential in bio- and optoelectronic applications.

Some inorganic compounds kill cancer cells upon light irradiation without a need for dioxygen to be present. To which clinical needs could these compounds respond?

An induction to the wonders of lanthanides, and a call for standardised methods for characterisation of lanthanide complexes in solution.

New perspectives for dinitrogen activation: an overview of photochemical pathways to cleave the strong N–N bond.

A summary of recent developments on the anticancer activity of complexes of rhenium, osmium, and iridium is described.

Radiometal based radiopharmaceuticals for imaging and therapy require selective ligands (bifunctional chelators, BFCs) that form metal complexes, which are inert against trans-chelation under physiological conditions, linked to a biological vector, directing them to the targeted tissue. Bispidine ligands with a very rigid backbone and widely variable donor sets are reviewed as an ideal class of BFCs, and recent applications are discussed.

This perspective deals with the synthesis and study of SMM properties of heterometallic 3d–4f complexes containing diamagnetic 3d metal ions.

A step-by-step investigation to move TTA-UC from homogeneous solutions to nanostructured solid materials for new technological perspectives.

This perspective highlights recent advances in the field of PbS NC-sensitized near-infrared-to-visible upconversion based on triplet–triplet annihilation in rubrene.

This review primarily introduces new progress in preparation strategies of ultrasmall (<10 nm) NaREF₄ upconversion nanoparticles, and their use in imaging and drug delivery.

Dye-sensitized solar cells (DSSCs) have been deemed as promising alternatives to silicon solar cells for the conversion of clean sunlight energy into electricity.

Can metalloporphyrins be used in a dual absorber-upconverter capacity to improve photovoltaic efficiency?

Multifunctional molecular materials exhibiting electrical conductivity and single-molecule magnet (SMM) behaviour are particularly attractive for electronic devices and related applications owing to the interaction between electronic conduction and magnetization of unimolecular units.

This perspective reviews our recent efforts towards the self-assembly of polynuclear clusters with ditopic and tritopic multidentate ligands HL¹ (2-phenyl-4,5-bis{6-(3,5-dimethylpyrazol-1-yl)pyrid-2-yl}-1H-imidazole) and H₂L² (2,6-bis-[5-(2-pyridinyl)-1H-pyrazole-3-yl]pyridine), both of which are planar and rigid molecules.

The platinum chemotherapy drugs cisplatin, carboplatin, and oxaliplatin are known to cause seven different types of side effects in patients.

In this Perspective article, we highlight emerging opportunities for the rational design of catalysts upon the choice, exchange, partial removal or pyrolysis of ligands.

Approaches to the visible light photo-sensitisation of organic–inorganic hybrid polyoxometalates are presented and future trends discussed.

This perspective summarizes the utilization of α-aminophosphines as monodentate and bidentate ligands in the synthesis of platinum, palladium and rhodium complexes.

We overview recent advances in the mechanisms at and near the Ni–Fe sites of [NiFe] hydrogenases for activation–inactivation, catalytic reaction, proton transfer, and O₂-tolerance.

Chiral metal-based drugs are currently an interesting and rapidly growing field in anticancer research. Here the different chiral metal-based anticancer agents and the extent to which the chiral resolution affects their biological properties are discussed. This review will aid the design of new potent and efficient chiral metal-based anticancer drugs that exploit the unique properties combined with their potential selectivity toward targeted chiral biomolecules.

Organometallic and metal amide reagents react with –OH groups to generate metal–oxygen connectivity, yielding metal-oxo heterobimetallics, clusters and nanoparticles.

Equilibrium binding constants are now readily accessible for metalation of metallothioneins.

Mechanochemical methods (solid–solid reactions under ambient conditions or solvent free synthesis) are useful for the preparation of intercalation compounds.

High quality bulk samples of the first four polyacenes, naphthalene, anthracene, tetracene, and pentacene, doped with alkali metal in 1 : 1 and 1 : 2 stoichiometries were prepared and their fundamental properties were systematically studied. The carrier doped typical aromatic hydrocarbons showed a large variety of properties as well as charge transfer complexes and metal doped fullerides. We open a new category in condensed matter chemistry and physics.

Alcohol and amine intercalates with hosts based on alkaline-earth metal phenylphosphonates are reviewed.

This review lists some relevant types of intercalated lamellar materials and applications of DFT calculations in these materials.

Dion–Jacobson perovskites and their exfoliated nanosheets provide a unique platform for designing new dielectric/ferroelectric materials.

Metal–organic frameworks (MOFs), also known as coordination polymers, have attracted extensive research interest in the past few decades due to their unique physical structures and potentially vast applications.

Metalloenzymes can catalyze the oxidation of hydrocarbons with high efficiency and selectivity. For this reason, they are taken as inspiration for the development of new catalyst. A promising strategy is the combination of metal coordination complexes and peptide chains. The use of metallopeptides in oxidation reactions is discussed.

Charge distribution changes in Bi- and Pb-3d transition metal perovskite type oxides were examined. The change in the depth of the d level of the transition metal causes the intermetallic charge transfer.

Incorporating photosensitive molecules into the organic/inorganic hybrid materials can contribute to forming photoresponsive systems.

The isolobal relationships of BCO/CH and CO/H⁻ are applied to bridge boron carbonyls and the well-known hydrocarbon molecules.

Here we discuss the emerging field of luminescent lanthanide-based soft materials with our focus on the different approaches used for their design and synthesis as well as manipulations of their functional properties.

This Frontier article reviews recent advances on the excited state reactivity of earth-abundant metal–oxygen complexes.

This Frontier article highlights the recent development and advances in designing ferric phosphide (FeP) based composite materials for the HER.

Recent advances in the all-abundant-element molecular devices for solar-driven H₂ generation via intramolecular processes are overviewed including their assembly approaches, and structure–catalytic activity relationships.

This frontier article introduces recent developments and applications of iridium(III) complexes as luminescent probes for ions and biomolecules.

Unusual, if not unprecedented, effects of transition-metal ions and ligands are discovered when simple metal oxides or carbides activate methane in the gas phase in manners reminiscent of oriented external electric fields.

Most recent developments in Zintl cluster chemistry are highlighted, including advances in understanding of their formation and their use as sources for nanostructured materials.

While rhodium has no known natural biological function, the element's unique structural and reactivity properties make for unique opportunities in biological systems.

This Frontier illustrates a brief personal account on the effect of heme–heme interactions in dihemes which thereby discloses some of the evolutionary design principles involved in multiheme proteins for their diverse structures and functions.

Metal complexes based on iridium metal centers have attracted attention as probes due to their tunable biological and chemical characteristics.

Synthesis, structure and reactivity of cyclobutane-1,3-diyl and cyclopentane-1,3-diyl analogues are discussed along with their application as molecular switches or reagents to activate or trap small molecules with single or multiple bonds.

Among the various strategies for achieving high solar energy utilization, elemental doping has been extensively explored owing to its advantages in regulating light absorption, band positions and charge carrier processes of photocatalysts.

Surface and interface structures are considered as the critical parameters which can be engineered to improve the performance of catalysts. This Frontier article highlights our recent advances in surface and interface design toward photocatalytic water splitting.

Transition-metal carbodiimides have emerged as energy materials, both as anodes in rechargeable batteries and as catalysts in photochemical water oxidation.

We discuss synthetic strategies and applications of highly ordered bioinorganic materials based on crystalline protein scaffolds.

Recent achievements in the preparation, characterization and reactivity of gold(III) complexes of alkenes, alkynes and arenes are presented and discussed.

Recent developments in main group chemistry towards the activation and conversion of N₂ have lead to the revelation that boron can greatly affect these processes.

Upconversion photodynamic therapy uses sequential multiphoton absorption by transition metal nanoparticles (NaYF₄/Yb³⁺/Er³⁺) to allow FRET excitation of traditional visible light-absorbing photosensitizers by deeply penetrating near infrared light (810 nm or 980 nm).

After bulk solids and nanoparticles, examples of upconversion are now emerging at the discrete molecular scale in solution.

A brief review on recent developments in the field of TM-substituted POM water oxidation catalysts was systematically presented, providing researchers valuable guidance for further discovery and improvements in efficient and robust TSPWOCs in future.

Electrochemical oxidation of small molecules such as ethanol, methanol and formic acid on Pd based compounds has a great impact on green energy production in fuel cells.

This Frontier article highlights the utilization of phosphorescent iridium(III) complexes for biosensing and photodynamic therapy.

The emerging field of siliconoid clusters is reviewed and a parameter ϕ introduced that distinguishes hemispheroidal and regular coordination of vertices.