Tuning PtII‐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(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 amo...

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Veröffentlicht in:Chemistry : a European journal Jg. 26; H. 6; S. 1314 - 1327
Hauptverfasser: 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
Sprache:Englisch
Veröffentlicht: Weinheim Wiley Subscription Services, Inc 27.01.2020
John Wiley and Sons Inc
Schlagworte:
Antibiotics
Chemistry
Coordination compounds
Coupling (molecular)
Dehydrogenation
Density functional theory
donor–acceptor systems
Electrochemistry
Electrochromism
Electron flux density
Ligands
Oxidation
Oxygen
Photocatalysis
Photochemicals
Platinum
Pyridines
redox-active ligands
spectroelectrochemistry
Sulfonamides
Time dependence
ISSN:0947-6539, 1521-3765, 1521-3765
Online-Zugang:Volltext
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Zusammenfassung: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. Outcomes of ligand design: A series of platinum‐based donor–acceptor complexes is presented. The effect of the donor ligands on the frontier orbitals, redox potentials, redox‐induced isomerism, and photocatalysis is probe.
Bibliographie:Dedicated to Professor Goutam K. Lahiri on the occasion of his 60th birthday
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.201903700