Carbazole-functionalized poly(1-phenyl-1-alkyne)s were synthesised in high yields with high molecular weights by transition metal-catalysed acetylene polymerisation. All the polymers possessed high thermal stability and emitted strong photo-and electroluminescence. They were photosensitive and could be readily photo-oxidized to generate fluorescent patterns.

Fluorescent nanodiamonds are attractive for biological applications because of their biocompatibility and stable photoluminescence. Chemical and air oxidation treatments were used to produce small (~15 nm) nanodiamonds containing a single fluorescent centre. These were both physically and optically characterised and then used as a donor for single-molecule Förster resonance energy transfer.

Key to elucidating the origin of catalytic activity and improving catalyst design is determining molecular-level structure, in both the ‘resting state’ and in the functioning ‘active state’ of the catalysts. Herein, we explore some of the analytical challenges important for designing and studying new catalytic materials for making and using hydrogen.

2-(Di-2-pyridylamino)pyrimidine forms mononuclear trans-[Fe(NCS)₂(L)₂], [Cu(L)₂(H₂O)](BF₄)₂·H₂O and [PdCl₂(L)] complexes, a dinuclear [(PdCl₂)₂(L)]·¾H₂O complex, and a discrete [Ag₂(L)₄](PF₆)₂ metallomacrocycle. trans-[Fe(NCS)₂(L)₂] undergoes a temperature-dependent spin crossover, which was examined by magnetic and structural measurements.

Using the example of solar fuels research at the Chemistry Biology Centre (KBC) at Umeå University, Sweden, an institutional approach is described to promote interdisciplinary research by breaking down traditional departmental borders.

Members of a family of iron(II) complexes of a dipyridylamino-substituted triazine ligand (DTAC) of formula [Fe(DTAC)₂(anion)₂], display high-spin structural and magnetic features when anion = NCS and NCSe and spin-crossover behaviour when anion = N(CN)₂ and NCBH₃.

The static and dynamic aspects of supramolecular interactions between coumarin 153 (C153) and fluorescein (FL) with bovine serum albumin (BSA) has been determined by steady-state absorption, fluorescence, fluorescence resonance energy transfer, site marker competitive experiments, and a molecular docking study. It has been revealed that C153 binds to domain IIIA of BSA whereas FL binds non-specifically. Kinetics of binding has also been studied by stopped-flow method.

A novel Mn(II)–phosphate coordination polymer has been synthesized under hydrothermal conditions. The complex has a novel 3D non-interpenetrated novel pkb1 network that exhibits spin-canted antiferromagnetism at low temperature.

A straightforward, practical and cost-effective method for the synthesis of Fmoc/Boc-protected peptide nucleic acid (PNA) monomers from N-(2-(Fmoc)aminoethyl)glycinate ethyl ester is described. The Fmoc/Boc strategy was developed in order to eliminate the solubility issues, in particular that of the cytosine monomer, that often occur during the solid-phase synthesis of PNA.

Photochemical upconversion is applied to solar cells in the presence of a backscatter to double the efficacy of the device.

A novel biodegradable amphiphilic dendritic polyether-ester whose building blocks (glycerol, glycolic acid oligomer and methoxy poly(ethylene glycol)) are known to be biodegradable or biocompatible is described. This biodendritic macromolecule is of interest for fundamental physiochemical studies and as a new tailored material for applications in drug delivery and tissue engineering.

Even a non-degassed solution of benzil exhibits phosphorescence at room temperature in ionic liquids due to low solubility of oxygen in these media compared with the conventional molecular solvents. The existence of multiple conformers in frozen conditions has been established by the excitation wavelength dependence of the phosphorescence spectra at liquid nitrogen temperature.

Feedback mechanisms originating from autocatalytic events near the end of an electron transfer chain can improve the rate of electron transfer nearer to the beginning, leading to cooperative multi-electron transfer.

Three naphthaledene Schiff bases were analysed by variable temperature X-ray crystallography and solid state electronic spectra. The crystal structures showed no significant changes despite the compounds changing colour with temperature. The major contribution to the colour change is the broadening of the absorption band and not the change in enol-keto composition.

Eight square pyramidal copper complexes and four square planar palladium complexes with general structure [Cu(I_L)(A_L)H₂O]²⁺, were synthesised. The crystal structures of [Cu-PHENSS](ClO₄)₂·H₂O and [Cu-56MESS](ClO₄)₂·1.5H₂O are reported. The copper complexes display some anticancer and antibacterial activity. The palladium complexes all have IC₅₀ values of ~10 μM in the L1210 cell line and minimal antibacterial activity.

Dye-sensitized solar cells (DSSCs) have been investigated extensively as promising candidates for renewable-energy systems. With various heterocycles incorporated into the dye sensitizers, different solar-cell performances are obtained. This review focuses on recent progress in the molecular design of heterocyclic-functionalized organic dyes for efficient DSSCs, and special attention has been paid to the relationship between the properties and the structures of the heterocyclic-functionalized organic dyes.

A poly(acrylic acid) thin film with embedded Ag nanoparticles demonstrates pH-induced variation of plasmonic properties due to the change of distance between Ag nanoparticles during swelling and shrinking of the polymer matrix. Dynamic plasmonic properties should be applicable for optoelectronic devices and sensors.

Ion mobility-mass spectrometry (IM-MS) provides a biophysical approach well suited for structural analysis of proteins and their complexes with conformational heterogeneity. Here we have utilised negative mode IM-MS to investigate structural transitions of calmodulin upon Ca²⁺ and target peptide binding. Of particular importance is the ability to detect conformations of calmodulin-peptide complexes without a full complement of calcium.

Six homo- and heteroleptic bismuth(iii) thiobenzoates of form Ph_3-nBiL_n (n = –3) have been synthesised by solvent-mediated and solvent-free methods. The structures of the compounds derived from thiobenzoic acid have been determined by X-ray crystallography. Bactericidal studies against three strains of Helicobacter pylori show a minimum inhibitory concentration of 6.25 µg mL^–1 for all compounds, indicating that the high activity is independent of ligand type and degree of substitution at the Bi(iii) centre.

In natural light-harvesting systems, pigment-protein complexes (PPC) convert sunlight to chemical energy with near unity quantum efficiency. Studies using two-dimensional electronic spectroscopy (2DES) provide an incisive tool to probe the electronic, energetic, and spatial landscapes that enable the efficiency observed in photosynthetic light-harvesting. We review design principles of PPCs learned from the information contained within 2D spectra.

A new radical of 2-(2-quinoxalinyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide was first designed and synthesised to afford four coordination sites to construct Cu^II and Mn^II complexes with more complicated structures and magnetic properties.

A simple and efficient strategy for the synthesis of 6-substituted-2-pyrone derivatives in good yield by BF₃·OEt₂ mediated one pot cyclization and keto-protection of δ-hydroxy-β-keto esters obtained via regioselective addition of 1, 3-dicarbonyl dianion of ethyl acetoacetate to aldehydes and ketones is described.

A range of alkaline earth and lanthanoid complexes involving new substituted pyrazolates of the type [M(pz)_x(solv)_y] were prepared. They were structurally and spectroscopically characterized. Also, the first transoid lanthanoid iodo pyrazolate complex, [Ln^II(pz)I(thf)₄], was isolated.

Three new Ln-MOFs, [Tb(HPIA)(PIA)(H₂O)₂]_n·0.5nH₂O (1), [Eu(HPIA)(PIA)(H₂O)₂]_n·0.5nH₂O (2), and [Tb₂(PIA)₃(H₂O)₄]_n·3nH₂O (3) (H₂PIA = 5-(pyridin-4-yl)isophthalic acid), have been obtained by DMF/H₂O volume-ratio-controlled assembly and structurally characterised. The thermal and photoluminescence properties of complexes 1-3 in the solid state have also been investigated.

Geometry, electron density, and electron localizability properties are used to clarify the nature of unusual hydrogen bonding to the siloxane linkage in a computational study. It is described how the basicity of the siloxane linkage can be significantly increased through variation of the Si–O–Si bond angle and how this is reflected in corresponding indicators of hydrogen bonding.

Intermolecular attractive forces that are considerably weaker than hydrogen bonding and coordination complexation may be used in the design of new molecules that function as host molecules in the solid-state. High levels of prediction are possible, and X-ray crystallographic analysis provides a rich source of information about new and previously hidden supramolecular synthons.

This article reviews some of the recent work in the field of water oxidation and reduction catalysts by fellows and associates of the Australian Research Council’s Centre of Excellence for Electromaterials Science (ACES) at Monash University and the University of Wollongong, as well as their collaborators. This work is focussed on the development of a hydrogen-based energy technology. Topics discussed include: (1) the role and apparent relevance of the cubane structure of the Photosystem II - Water Oxidation Complex (PSII-WOC) in non-biological homogeneous and heterogeneous water oxidation catalysts, (2) light-activated conducting polymer catalysts for both water oxidation and reduction, and (3) porphyrin-based light harvesters and catalysts.

We use an information-theoretic, extrathermodynamic approach to analyse the changes in the electronic structure between analogous methine and azomethine dyes.

The addition of Cu(ii) to a solution of curcumin in acetonitrile enables the initial complexation of Cu(ii); a subsequent internal reduction of Cu(ii) to Cu(i) oxidises curcumin to a curcumin radical, leading to decomposition of curcumin.

A combined computational and experimental study demonstrated that the protonation states of key acidic residues in the binding sites have both structural and energetic impacts on the function of the Na/K pump at the E2•Pi state.

Enzymes allow efficient conversion of biomass into useful chemical energy; however, they are seldom optimized for reaction conditions in biotechnology. Directed molecular evolution can be used to generate enzymes suited for new environments. As an example, we illustrate how yeast pyruvate decarboxylase 1 has been enhanced for in vitro fermentative glycolysis.

The solution behaviour of nickel complexes of bis(benzimidazolin-2-ylidene)pyridine pincer ligands suggests an equilibrium between four- and five-coordinate complexes.

Surface modification of TiO₂ with molecular metal oxide clusters is demonstrated to be a promising approach for providing it with visible-light responsiveness or enhancing the UV response.

Quadratic optical non-linearities of gold alkynyl complexes increase on π-system lengthening and on introduction of electron-releasing substituents on the π-bridge ring adjacent to the metal centre, while maximal values of the effective two-photon absorption cross-sections of 1,4-{(PCy₃)Au(C≡C)}₂C₆H₄ and {(PCy₃)Au(C≡C-4-C₆H₄C≡C)}₆C₆ increase non-linearly on proceeding from linear complex to 6-fold-symmetric complex.

Future requirements for water splitting technologies need highly efficient water oxidation catalysts that are sufficiently stable for operation over many years. In this paper, we discuss some of the chemical and thermodynamic challenges confronting this goal, as well as some of the strategies that are available to overcome them.

Palladium-catalyzed [4 + 1] type annulations leading to dibenzofulvenes are reported, which involve double cross-coupling reactions of 1,1-diborylalk-1-enes with 2,2′-dibromobiaryls and of 9-stannafluorenes with 1,1,-dibromoalk-1-enes.

The Mn₄/Ca centre in Photosystem II is the most effective anodic water oxidizing catalyst known and operates close to the thermodynamic limit. This performance derives from redox properties of Mn in the oxidation states II–IV, which are uniquely ‘tuned’ to allow function with minimum overvoltage. Possible strategies to exploit this for efficient, biomimetic electrolytic H₂ generation are discussed.

Lanthanoid complexes of 5-(2′-pyridyl)tetrazole are unexpectedly isolated as hydrates, despite being crystallized in the presence of dimethyl sulfoxide.

There is growing evidence that interactions between the amyloid-beta peptide Aβ(1-42) and neuronal cell membranes and copper are involved in Alzheimer’s disease (AD) pathogenesis. Our data support the finding that ternary interactions between Cu²⁺, lipids, and Aβ(1-42) may have significance in AD, and illustrate the importance of using appropriate lipid membrane composition.

The 2 : 1 tetrahedral complexes of the bidentate diphosphine ligands cis-bis(diphenylphosphino)ethene (dppey), cis-bis(diphenylphosphino)ethane (dppe), and cis-bis(diphenylphosphino)propane (dppp) with copper(i), silver(i), and gold(i) have been synthesized as tetraphenylborate salts and characterized by NMR spectroscopy, electrospray mass spectrometry, and single crystal X-ray structure determinations at 200 K.

Reactions of Group 7 dinuclear complexes [M₂(CO)₆(μ-pyS)₂] (M = Mn, Re) with (Ph₃P)₂Ni(CO)₂ have been investigated.

MEH-PPV forms a variety of mesoscale structures depending on chain length, solvent quality, and chemical defect concentration.

Photoelectron spectroscopy and ab initio calculations are used to interrogate the bromide–carbon monoxide gas phase complex, Br^-···CO. A new minimum was found for the neutral complex, namely a linear Br···OC form. The electron affinity of the Br···CO complex is 3.50 ± 0.05 eV.

An X-ray crystallographic study using two different radiation wavelengths was performed on 7-diethylamino-[1',3′,3′-trimethyl-4-((1,3,3-trimethyl-1,3-dihydro-2H-indole-2-ylidene)methyl)-1',3,3′,4-tetrahydrospiro[chromene-2,2'-indole]] crystals obtained from the condensation of two molecules of Fischer’s base with 4-(dimethylamino)salicylaldehyde. No significant deviations between the final models were observed.

The Fe(ii) template synthesis of a new tripodal tris-bipyridine ligand derivative incorporating a nitrogen bridgehead is reported. The pseudo cage-like structure encapsulates both a proton and an Fe(ii) ion in its cavity and forms an extended helical arrangement ‘capped’ at its open end by a hydrogen bonded PF₆^– ion.

Organometallics with various donor–bridge–acceptor arrangements allow investigation of the key factors affecting the properties of these multifunctional molecular systems. Herein, reactions of 7,7,8,8-tetracyanoquinodimethane (TCNQ) with Fe(C≡CR)(dppe)Cp* and Ru(C≡CR)(PPh₃)₂Cp (R = H, Ph) are described. Formed are the mono-cation (by oxidation in the iron series), zwitterionic complexes, and complexes formed by regioselective [2 + 2]-cycloaddition and subsequent ring-opening reactions; elimination of HCN (in the ruthenium series) was also observed.

Reaction of the labile cluster [Os₃(CO)₁₀(NCMe)₂] with 2,2′-benzothiazyl disulfide has been studied. Three new triosmium clusters have been synthesized and structurally characterized from this study.

Rubidium and caesium orthanilates form chemically stable two-dimensional layered coordination polymeric structures based on stereochemically variable metal centres: six-, seven-, eight- and ten-coordinate in the rubidium complex and seven-coordinate in the caesium complex, these compounds representing rare examples of structurally characterized metal complexes with orthanilic acid.

A multi-component bi-layer complex involving 1,4-bis(triethylammoniomethyl)benzene cation, p-sulfonatocalix[4]arene anion and phosphonium cation shows the preferential binding of the bis-triethylammonium cation in the cavity of two geometrically opposed calixarenes with the same molecular capsules persisting in solution.

Nanochemical design methods offer routes to overcome the thermodynamic and kinetic hurdles associated with solid state storage in hydrides. In this review we discuss strategies of nanosizing, nanoconfinement, morphological/dimensional control, and application of nanoadditives on the hydrogen storage performance of metal hydrides and the potential role of such materials in a sustainable hydrogen cycle.