Tuning Pt II ‐Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals, Redox Potentials, UV/Vis/NIR Absorptions, Electrochromism, and Photocatalysis

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...

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Published in:Chemistry : a European journal Vol. 26; no. 6; pp. 1314 - 1327
Main Authors: Sobottka, Sebastian, Nößler, Maite, Ostericher, Andrew L., Hermann, Gunter, Subat, Noah Z., Beerhues, Julia, Behr‐van der Meer, Margarethe, Suntrup, Lisa, Albold, Uta, Hohloch, Stephan, Tremblay, Jean Christophe, Sarkar, Biprajit
Format: Journal Article
Language:English
Published: Germany Wiley-VCH Verlag 27.01.2020
Subjects:
Chemical Sciences
or physical chemistry
Physics
Quantum Physics
Theoretical and
redox-active ligands
spectroelectrochemistry
donor-acceptor systems
platinum
electrochemistry
ISSN:0947-6539, 1521-3765
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Summary: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.
Bibliography:PMCID: PMC7027812
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201903700