Volume 24, Issue 49 p. 13020-13025
Full Paper

Stereocontrolled Photoinduced Electron Transfer in Metal-Fullerene Hybrids

Dr. Anton J. Stasyuk

Corresponding Author

Dr. Anton J. Stasyuk

The Institute of Computational Chemistry and Catalysis, and Department of Chemistry, University of Girona, C/ Maria Aurèlia Capmany 69, 17003 Girona, Spain

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Dr. Olga A. Stasyuk

Dr. Olga A. Stasyuk

Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, 166 10 Prague, Czech Republic

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Dr. Salvatore Filippone

Dr. Salvatore Filippone

Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, 28040 Madrid, Spain

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Prof. Dr. Nazario Martin

Prof. Dr. Nazario Martin

Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, 28040 Madrid, Spain

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Prof. Dr. Miquel Solà

Corresponding Author

Prof. Dr. Miquel Solà

The Institute of Computational Chemistry and Catalysis, and Department of Chemistry, University of Girona, C/ Maria Aurèlia Capmany 69, 17003 Girona, Spain

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Prof. Dr. Alexander A. Voityuk

Corresponding Author

Prof. Dr. Alexander A. Voityuk

The Institute of Computational Chemistry and Catalysis, and Department of Chemistry, University of Girona, C/ Maria Aurèlia Capmany 69, 17003 Girona, Spain

Institució Catalana de Recerca i Estudis Avancats, 08010 Barcelona, Spain

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First published: 29 June 2018
Citations: 17

Graphical Abstract

Stereospecific effect: Stereoisomers of an Ir-complex demonstrate clearly different charge transfer properties under photoexcitation, as shown by this exhaustive DFT computational study.

Abstract

Photoinduced electron transfer in transition-metal complexes linked to a fullerene moiety is of increasing interest. Recently, several stereoisomers of an Ir-complex exhibiting configurational stability at metal center, which does not undergo epimerization have been synthesized (Angew. Chem. Int. Ed. 2017, 56, 2136). The presence of multiple electron donor and acceptor sites located at opposite ends with respect to the metallic center creates the prerequisites for the formation of entirely different charge transfer (CT) states. Here we report the results of quantum mechanical calculations and detailed analysis of excited-state properties for all stereoisomers of the junction. We found that the stereoisomers demonstrate clearly different CT properties by photoexcitation. The found photo-stereospecific effects can be used to design new hybrids with a different type of photoinduced CT state, exhibiting dissimilar activity in photocatalysis.

Conflict of interest

The authors declare no conflict of interest.