Dalton Transactions : An International Journal of Inorganic Chemistry

Potassium borate glass has great potential as an ion transport material. The ion transport rate is closely related to the microstructure of the glass. However, the disorder and variations in boron and oxygen atom types in the glass structure pose challenges in the analysis of this complex glass structure. In this work, the structure of potassium borate glass was unveiled through the neutron diffraction method and ab initio molecular dynamics (AIMD) simulations. The B-O, K-O, and O-O atomic interactions, bond lengths, coordination numbers, cavity distribution, ring structure distributions and other detailed information in the microstructure of potassium borate glass were obtained...

Two new spin crossover (SCO) Fe(III) compounds were prepared, their structures were analysed and their magnetic properties were investigated. An exhaustive analysis of the effects of halogen substitution and aromatic ring functionalisation on the magnetic properties of non-solvated Fe(III) perchlorate complexes has been performed. Through comparative analysis, different magnetic profiles were found for the compounds studied, namely F (1), Cl (2), H (3), Br (4a, 4b), and I (5). Using tools like Hirshfeld analysis, the study revealed patterns in octahedral distortions and deviations from the ideal octahedral geometry...

Molecular junctions, which involve sandwiching molecular structures between electrodes, play a crucial role in molecular electronics. Recent advances in this field have revealed the vital role of organometallic chemistry in the investigation of molecular junctions, which has added to their well-known contributions to catalysis and materials chemistry. This review summarizes the recent examples of organometallic chemistry applications in molecular junctions, which can be categorized into three types, i.e. , class I encompassing molecular junctions with bridging organometallic complexes, class II involving molecular junctions with covalent and noncovalent metal electrode-carbon bonds, and class III comprising organometallic reactions within molecular junctions...

Leveraging solar energy through photocatalytic hydrogen production from water stands out as one of the most promising approaches to address the energy and environmental challenges. The choice of catalyst profoundly influences the outcomes of photocatalytic reactions, and constructing heterojunctions has emerged as a widely applied strategy to overcome the limitations associated with single-phase photocatalysts. MoO3 , renowned for its high chemical stability, encounters issues such as low photocatalytic efficiency and fast recombination of photogenerated electrons and holes...

The Lewis basicity of a μ3 -oxo ligand for (μ3 -O)[Rh(cod)]3 (μ4 -O)M (cod = 1,5-cyclooctadiene) complexes was controllable by metal species on the μ4 -oxo ligand locating at the opposite site of the μ3 -oxo ligand. Coordination of the μ3 -oxo ligand of [(μ3 -O){Rh(cod)}3 (μ4 -O){Au(PPh3 )}][BF4 ] (1) to [Au(PPh3 )]+ indicated sufficient Lewis basicity of the μ3 -oxo ligand in 1 to form [{(Ph3 P)Au}(μ3 -O){Rh(cod)}3 (μ4 -O){Au(PPh3 )}][BF4 ] (2)...

Ligand steric hindrance and electronic effects play a crucial role in late-transition metal-catalyzed olefin polymerization. In this research, a series of o -aryl halogenated α-diimine ligands bearing bulky dibenzhydryl substituents, along with their corresponding nickel catalysts, have been synthesized and thoroughly characterized. The nickel catalysts demonstrated very high activity in ethylene polymerization, achieving a high rate of up to 107 g mol-1 h-1 . The produced polyethylenes displayed a broad spectrum of molecular weights (12...

A series of Ir(III)-naproxen (NPX) conjugates with the molecular formula [Ir(C^N)2 bpy(4-CH2 ONPX-4'-CH2 ONPX)](PF6 ) (Ir-NPX-1-3) were designed and synthesized, including C^N = 2-phenylpyridine (ppy, Ir-NPX-1), 2-(2-thienyl)pyridine (thpy, Ir-NPX-2) and 2-(2,4-difluorophenyl)pyridine (dfppy, Ir-NPX-3). Cytotoxicity tests showed that Ir-NPX-1-3 exhibited excellent antitumor activity, especially in A549R cells. The cellular uptake experiment showed that the complexes were mainly localized in mitochondria, and induced apoptosis in A549R cells by damaging the structure and function of mitochondria...

In this work, we address the synthesis of stable spin-crossover nanoparticles capable of undergoing a hysteretic spin transition at room temperature. For this purpose, we use the reverse-micelle protocol to prepare naked [Fe(NH2 trz)3 ](NO3 )2 and core@shell [Fe(NH2 trz)3 ](NO3 )2 @SiO2 nanoparticles. Through meticulous adjustment of synthetic parameters, we achieved nanoparticle sizes ranging from approximately 40 nm to 60 nm. Our findings highlight that [Fe(NH2 trz)3 ](NO3 )2 presents a modest thermal hysteresis of 7 K, which decreases by downsizing...

Plasma treatment as an effective strategy can simultaneously achieve surface modification and heteroatom doping. Here, an N/P-doped NiFeV oxide nanosheet catalyst (N/P-NiFeVO) constructed by Ar/PH3 plasma treatment is used to drive the oxygen evolution reaction (OER). The introduction of V species leads to the formation of an ultrathin ordered nanostructure and exposure of more active sites. Compared to the 2D NiFeV LDH, the prepared N/P-NiFeVO by plasma treatment possesses multiple-valence Fe, V and Ni species, which regulate the intrinsic electronic structure and enable a superior catalytic activity for the OER in alkaline media...

This work describes a new well-defined, air-stable, phosphine free palladium(II) [Pd(L)Cl] (1) catalyst. This catalyst was utilized for N -alkylation of amines and indole synthesis where H2 O was found to be the by-product. A broad range of aromatic amines were alkylated using this homogeneous catalyst with a catalyst loading of 0.1 mol%. Greener aromatic and aliphatic primary alcohols were utilized and a hydrogen auto-transfer strategy via a metal-ligand cooperative approach was investigated. The precursor of the antihistamine-containing drug molecule tripelennamine was synthesized on a gram scale for large-scale applicability of the current synthetic methodology...

Direct ethanol fuel cells (DEFCs), which have been widely recognized as nontoxic and green energy conversion devices, show attractive application prospects for liquid hydrogen-carriers, due to the higher specific energy and lower toxicity of ethanol. Pt-based catalysts are widely used in DEFCs, while their poor poisoning resistance highlights the importance of composition and structure optimization. Herein, we synthesized a series of reduced graphene oxide supported ternary alloy Au x Pt1- x Cu3 /rGO ( x = 0-1) catalysts with excellent ethanol oxidation performance and a composition-dependent volcano plot trend of the ordering degree was observed and rationalized...

Lanthanide luminescence is characterised by "forbidden" 4 f- 4 f transitions and a complicated electronic structure. Our understanding of trivalent lanthanide(III) ion luminescence is centered on Eu3+ because absorbing and emitting transitions in Eu3+ occur from a single electronic energy level. In Sm3+ both absorbing and emitting multiplets have a larger multiplicity. A band arising in transitions from the first emitting state multiplet to the ground state multiplet will have nine lines for a Sm3+ complex...

The structural features of cobalt-based oxygen evolution catalysts are elucidated by combining high-field MAS NMR spectroscopy and DFT calculations. The superior photocatalytic activity of the heterogeneous system over its homogeneous counterpart is rationalised by the structural features. The higher activity is caused by a more favourable electron-withdrawing character of the framework.

Interfacial engineering emerges as a potent strategy for regulating the catalytic reactivity of metal phosphides. Developing a facile and cost-effective method to construct bifunctional metal phosphides for highly efficient electrochemical overall water splitting remains an essential and challenging issue. Here, a multiphase transition metal phosphide is constructed through the direct phosphorization of a Ni-Co metal-organic framework grown on nickel foam (Ni-Co-MOF/NF), which is prepared by utilizing nickel foam as conductive substrate and nickel source...

Hybrid phosphines usually combine a phosphine moiety with another heteroatom secondary donor group in their structures while compounds equipped with hydrocarbyl π-donor moieties remain uncommon. This contribution reports the synthesis and structural characterization of the first P/π-allyl-chelating complexes that were obtained using the structurally flexible and redox-active ferrocene unit as the scaffold, viz . [PdCl(R2 PfcCHCHCH2 -η3 :κ P )] (1R; R = Ph and cyclohexyl (Cy); fc = ferrocene-1,1'-diyl)...

Immobilization of imidazole molecules as proton carriers into MOFs to facilitate proton conduction is a general strategy for developing high proton conductive materials. Herein, we designed two imidazole substituted phthalic acid ligands and constructed two novel MOFs, {[Zr6 (OH)16 (H3 L1 )4 ]Cl8 ·20H2 O} n [Zr-MOF; H3 L1 = 2-(1 H -imidazol-4-yl) methylaminoterephthalic acid] and {Gd(HCOO)(H2 L2 )2 } n [Gd-MOF; H3 L2 = 5-(1 H -imidazol-4-yl)methylaminoisophthalic acid] and fully studied their porous nature, stability and water-assisted proton conduction...

In this study, we investigated the hydrolytic condensation of 3-aminopropyldiethoxymethylsilane over different superacid catalysts. We found that cyclic tetrasiloxanes with different stereostructures (Am-CyTS-NNf2 and Am-CyTS-NHf2 ) could be selectively prepared in high yields (>95%) depending on the superacid catalyst employed (bis(nonafluorobutanesulfonyl)imide or cyclohexafluoropropane-1,3-bis(sulfonyl)imide). The single-crystal X-ray structural analyses of compounds in which amino groups of Am-CyTS-NNf2 and Am-CyTS-NHf2 were protected by the tert -butoxycarbonyl group revealed the formation of all- cis and cis - trans - cis cyclic tetrasiloxanes, respectively...

The development of integrated multi-catalyst processes has become of high interest to transform abundant feedstocks or environmental pollutants to commodity chemicals in a one pot, one pass fashion. Specifically, CO2 poses a large environmental burden and would thus be a desirable, relatively abundant C1 source in multi-step synthetic chemistry. Herein we disclose the synthesis of aldehydes from CO2 via the integration of electrochemical CO2 reduction (CO2 RR) and hydroformylation, taking advantage of the typically unwanted concomitant hydrogen evolution (HER) to generate the necessary CO and H2 needed for hydroformylation...

Selective recognition of fructosyl amino acids in water by arylboronic acid-based receptors is a central field of modern supramolecular chemistry that impacts biological and medicinal chemistry. Fructosyl valine (FV) and fructosyl glycyl histidine (FGH) occur as N-terminal moieties of human glycated hemoglobin; therefore, the molecular design of biomimetic receptors is an attractive, but very challenging goal. Herein, we report three novel cationic Zn-terpyridine complexes bearing a fluorescent N -quinolinium nucleus covalently linked to three different isomers of strongly acidified phenylboronic acids ( ortho -, 2Zn; meta -, 3Zn and para -, 4Zn) for the optical recognition of FV, FGH and comparative analytes (D-fructose, Gly, Val and His) in pure water at physiological pH...

Polyaniline (PANI) stands out as a highly promising conducting polymer with potential for advanced utilization in high-performance pseudocapacitors. Therefore, there exists a pressing need to bolster the structural durability of PANI, achievable by developing composite materials that can enhance its viability for supercapacitor applications. In this particular study, a pioneering approach was undertaken to produce a novel NiMn2 O4 /PANI supercapacitor electrode material. A comprehensive array of analytical techniques was employed to ascertain the structural configuration, morphology, oxidation states of elements, composition, and surface characteristics of the electrode material...