Spin density distribution after electron transfer from triethylamine to an [Ir(ppy)2(bpy)]+ photosensitizer during photocatalytic water reduction

Sergey I. Bokarev; Dirk Hollmann; Alexandra Pazidis; Antje Neubauer; Jörg Radnik; Oliver Kühn; Stefan Lochbrunner; Henrik Junge; Matthias Beller; Angelika Brückner

doi:10.1039/C3CP54922D

Spin density distribution after electron transfer from triethylamine to an [Ir(ppy)₂(bpy)]⁺ photosensitizer during photocatalytic water reduction†

Sergey I. Bokarev,*^a Dirk Hollmann,^b Alexandra Pazidis,^a Antje Neubauer,^a Jörg Radnik,^b Oliver Kühn,^a Stefan Lochbrunner,^a Henrik Junge,^b Matthias Beller^b and Angelika Brückner*^b

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* Corresponding authors

^a Universität Rostock, Institut für Physik, Universitätsplatz 3, 18055 Rostock, Germany
E-mail: sergey.bokarev@uni-rostock.de

^b Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-Str. 29a, 18059 Rostock, Germany
E-mail: angelika.brueckner@catalysis.de
Web: www.catalysis.de
Fax: +49 381-1281-51244

Abstract

The photoreduction of the bis(2-phenylpyridinato-)(2,2′-bipyridine)iridium(III) ion ([Ir(ppy)₂(bpy)]⁺), used as a photosensitizer in photocatalytic water splitting, by triethylamine was studied by means of UV/VIS, XANES, and EPR spectroscopies, supported by theoretical calculations at density functional theory (DFT) and complete active space self-consistent field (CASSCF/CASPT2) levels. The combination of these methods suggests a predominant bpy localization of the spin-density of the unpaired electron with notable delocalization to the Ir center. This is particularly evident from EPR and theoretical results and leads to broad EPR lines and a large anisotropy of the g-factor.

Physical Chemistry Chemical Physics

Spin density distribution after electron transfer from triethylamine to an [Ir(ppy)₂(bpy)]⁺ photosensitizer during photocatalytic water reduction†

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Spin density distribution after electron transfer from triethylamine to an [Ir(ppy)₂(bpy)]⁺ photosensitizer during photocatalytic water reduction

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Physical Chemistry Chemical Physics