Heterogenization of molecular chalcoxides for electro-& photochemical H production.

The endeavour to develop high-performance cost-effective catalytic systems with a minimal amount of active components and generation of hazardous waste is a significant and formidable step towards enhancing the hydrogen evolution reaction and the development of design principles with potential value in large scale applications. Here we investigate the heterogenization process of molecular chalcoxide catalysts and explore their electro- and photo-catalytic efficacy in driving the hydrogen evolution reaction (HER).

Modulating the Supramolecular Assembly of α-Cyclodextrin and Anderson-type Polyoxometalate through Covalent Modifications.

A series of unprecedented supramolecular complexes of covalently modified Anderson-type polyoxometalates (POMs) and α-cyclodextrins (α-CDs) have been obtained and characterized in solid state by single-crystal X-ray diffraction, and in aqueous solution using various techniques including H DOSY NMR, 2D NOESY H NMR, isothermal titration calorimetry (ITC), and electrospray ionization time-of-flight mass spectroscopy (ESI-TOF-MS). It has been demonstrated that the supramolecular assembly process could be modulated by different covalent modification modes of the Anderson POMs, giving rise to a new type of POM/α-CD complexes featuring organic-inorganic pseudo-rotaxane structures, which are in good contrast to those of POM/γ-CD complexes of poly-rotaxane structures. Moreover, it is delighted to find that these pseudo-rotaxanes of POM/α-CD complexes exhibit stable chirality in aqueous solution, which has not been accomplished in previously reported POM/CD assemblies.

Revitalisation of group IV metal-oxo clusters: synthetic approaches, structural motifs and applications.

Group (IV) metal oxo clusters represent a unique family of molecular species that are increasingly being utilized in applications ranging from catalysis and materials chemistry to electronics, and sensors. These clusters exhibit distinctive structural features, chemical reactivity, and electronic structure. Nevertheless, their full potential has yet to be fully realized due to the lack of deeper understanding regarding their structure and formation mechanisms, inherent traits, and intricacies in their design, which could ultimately enable significant customization of their properties and overall behaviour.

Solar Light CO Photoreduction Enhancement by Mononuclear Rhenium(I) Complexes: Characterization and Mechanistic Insights.

The catalytic efficacy of a novel mononuclear rhenium(I) complex in CO reduction is remarkable, with a turnover number (TON) of 1517 in 3 h, significantly outperforming previous Re(I) catalysts. This complex, synthesized via a substitution reaction on an aromatic ring to form a bromo-bipyridine derivative, = 2-bromo-6-(1-pyrazol-1-yl)pyridine, and further reacting with [Re(CO)Cl], results in the facial-tricarbonyl complex [ReL1(CO)Cl] (). The light green solid was obtained with an 80% yield and thoroughly characterized using cyclic voltammetry, nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectroscopy, and ultraviolet-visible (UV-vis) spectroscopy.

Electronic and Molecular Structures of a Series of Nickel Bis-1,1-Dithiolates.

A series of homoleptic Ni bis-1,1-dithiolates, [Ni(SCRR')] (R=CN, R'=CN, COEt, CONH, Ph, Ph-4-Cl, Ph-4-OMe, Ph-4-NO, Ph-3-CF, Ph-4-CF, Ph-4-CN; R=NO, R'=H; R=R'=COEt) have been synthesized from the reaction of the alkali metal salt of the ligand and nickel chloride, and isolated as tetraphenylphosphonium or tetrabutylammonium salts. The complexes were characterized by X-ray crystallography, high-resolution mass spectrometry, and infrared (IR), nuclear magnetic resonance (NMR) and electronic absorption spectroscopies. The molecular structures show a rigidly square planar Ni(II) center linking two four-membered chelate rings whose dimensions are constant across the series.