Abstract
Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q2−)] are presented in this work, in which pimp=[(2,4,6‐trimethylphenylimino)methyl]pyridine and Q2−=catecholate‐type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl‐substituted phenylendiamide ligands, which show redox‐induced linkage isomerism upon oxidation. Time‐dependent density functional theory (TD‐DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2−)] with Q2−=3,5‐di‐tert‐butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross‐dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox‐induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.
Highlights
We have presented a series of new platinum(II) donor–acceptor systems with the lesser used phenyliminomethylpyridine ligand and a focus on the influence of the donor ligand
The title compounds were extensively characterized by cyclic voltammetry and UV/Vis/NIR- and EPR spectroelectrochemistry
KGaA, Weinheim perimental absorption spectra nicely, and the dynamic electron fluxes in such systems were investigated for the first time
Summary
Group 10 metals in their d8 electronic configuration have served to synthesize a range of donor–acceptor metal complexes.[1,2,3,4,5] These compounds are usually characterized by intense ligand-to-ligand charge transfers (LL’CTs), which impart unique photochemical and photophysical properties on the resulting metal complexes.[2,6] Applications range from dye-sensitized solar cells to small molecule activation and catalysis.[4,7,8]. Special emphasis is put on the redox-induced reactivity of the systems featuring o-bis(sulfonamide) ligands in this work. This ligand class was described for the first time more than half a century ago,[15] the application of this highly tunable ligand class is still rather limited[16,17] and only one platinum complex has been reported.[18] For the most part, these reports discuss fundamental structural aspects of the complexes. Perutz and co-workers studied rhodium(III) complexes with symmetrically and asymmetrically sulfonylated bis(amido)benzenes for transfer hydrogenation, showing the catalytic applications of these ligands.[20,21,22] Interestingly, they observed the dimerization of the aforementioned rhodium compounds, in which the oxygen atoms of the sulfonyl group bridge two rhodium centers.[20] Kavallieratos and co-workers observed the
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