inorganic chemistry

PHOTOCHEMISTRY AND PHOTOCATALYSIS OF

RHENIUM(I) DIIMINE COMPLEXES

HIROYUKI TAKEDAa,b, KAZUHIDE KOIKEb,c, TATSUKI MORIMOTOd,

HIROKI INUMARUdand OSAMU ISHITANIb,d,e

aToyota Central R&D Laboratories, Inc., Nagakute, Aichi, Japan

bCore Research for Evolutional Science and Technology (CREST), Japan Science and

Technology Agency (JST), Kawaguchi, Saitama, Japan

cNational Institute of Advanced Industrial Science and Technology, Tsukuba, Ibaraki, Japan

dDepartment of Chemistry, Tokyo Institute of Technology, Tokyo, Japan

eResearch Seeds Program, Japan Science and Technology Agency (JST), Kawaguchi,

Saitama, Japan

I. Introduction 138
II. Photophysics of Rhenium(I) Diimine Complexes 139
A. Electronic Structure of Rhenium(I) Diimine Complexes 139
B. Photophysical Relaxation Process of Rhenium(I)
Diimine Complexes 141
C. Effect of Weak Interactions Between Ligands on Electronic
Structure 144
III. Photochemistry of Rhenium(I) Complexes 146
A. Photochemical CO Elimination Reaction of a Re(I)
Hexacarbonyl Complex 146
B. Re

Re, Re

M, and Re

C Bond Homolysis Reactions 147
C. Photochemistry of Re(I) Diimine Tetracarbonyl Complexes 148
D. Photochemical Ligand Substitution Reaction offac-[Re(Diimine)
(CO) 3 PR 3 ]þ 150
E. Multinuclear Rhenium(I) Complexes 160
F. Photochemical Reactions offac-Re(bpy)(CO) 3 Cl from
Higher Excited States 163
G. Photochemical Reactions of the Ligand in Re(I) Complexes 166
IV. Rhenium(I) Complexes as Highly Efficient Photocatalyst 167
A. Mononuclear Rhenium(I) Complexes 168
B. Reaction Mechanism 172
C. Multicomponent Systems 176
D. Ruthenium(II)–Rhenium(I) Supramolecular Photocatalysts 178
E. Light-Harvesting System with Periodic Mesoporous
Organosilica 180
Acknowledgments 181
References 182

137

INORGANIC PHOTOCHEMISTRY #2011 Elsevier Inc.
VOLUME 63 ISSN 0898-8838 / DOI: 10.1016/B978-0-12-385904-4.00007-X All rights reserved