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Tuning Pt II ‐Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals, Redox Potentials, UV/Vis/NIR Absorptions, Electrochromism, and Photocatalysis
Author(s) -
Sobottka Sebastian,
Nößler Maite,
Ostericher Andrew L.,
Hermann Gunter,
Subat Noah Z.,
Beerhues Julia,
Behrvan der Meer Margarethe,
Suntrup Lisa,
Albold Uta,
Hohloch Stephan,
Tremblay Jean Christophe,
Sarkar Biprajit
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201903700
Subject(s) - chemistry , density functional theory , photochemistry , redox , electrochromism , reactivity (psychology) , acceptor , pyridine , ligand (biochemistry) , electrochemistry , molecular orbital , electron donor , homo/lumo , catalysis , computational chemistry , inorganic chemistry , molecule , medicinal chemistry , organic chemistry , medicine , biochemistry , physics , alternative medicine , receptor , electrode , pathology , condensed matter physics
Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q 2− )] are presented in this work, in which pimp=[(2,4,6‐trimethylphenylimino)methyl]pyridine and Q 2− =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(Q 2− )] with Q 2− =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.