Correction: Redox-active ligand based Mn(i)-catalyst for hydrosilylative ester reduction

Correction for ‘Redox-active ligand based Mn(i)-catalyst for hydrosilylative ester reduction’ by Soumi Chakraborty et al., Chem. Commun., 2021, 57, 12671–12674, DOI: 10.1039/D1CC05614J.

Thermally Controlled Synthesis of Octahedral Rhenium Clusters with 4,4′-Bipyridine and CN− Apical Ligands

The selective preparation, structural and spectroscopic study of two new rhenium cluster complexes trans-[Re6S8(bpy)4(CN)2] and trans-[Re6S8(bpy)2(CN)4]2− (bpy = 4,4′-bipyridine) obtained by reactions of corresponding hexarhenium cyanohalides with molten bpy are reported. The complexes were crystallized as solvates, displaying supramolecular structures based on cluster units linked by numerous weak interactions with bpy molecules. The molecular compound trans-[Re6S8(bpy)4(CN)2] (1) is insoluble in water and common organic solvents, while the ionic compound trans-Cs1.7K0.3[Re6S8(bpy)2(CN)4] (2) is somewhat soluble in DMSO, DMF and N-methylpyrrolidone. The presence of the redox-active ligand bpy leads to the occurrence of multi-electron reduction transitions in a solution of 2 at moderate potential values. The ambidentate CN− ligand is the secondary functional group, which has potential for the synthesis of coordination polymers based on the new cluster complexes. In addition, both new compounds show a weak red luminescence, which is characteristic of complexes with a {Re6S8}2+ cluster core.

Tuneable photoluminescence of TBAPY-based Metal-Organic Complex

We report the synthesis of crystals of an organic metal complex based on a large redox-active ligand (tbapy) exhibiting luminescent properties. We have demonstrated the tuning of the luminescence of a Zn-based metal-organic complex, soaked in advance in dimethylformamide, with pumping light.

First d0 Metal-Catalyzed Alkyl–Alkyl Cross Coupling Enabled by a Redox-Active Ligand

Alkyl–alkyl cross coupling through well-defined mechanisms that allow for controlled oxidative addition, prevent beta-hydride elimination, and tolerate hindered electrophiles are still challenging. We describe the first report of a redox-active ligand-enabled alkyl–alkyl cross coupling using a d0 metal. This (tris)amido ScIII complex as well as the oxidized variant are thor-oughly characterized (NMR, X-ray, EPR, CV, UV-Vis, DFT). Insight into the likely radical nature of the mechanism is dis-closed. Additionally, a substrate scope that includes functional groups incompatible with late transition metal catalysis, and both coupling partners bearing beta-hydrogens is reported.

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.