Photochemistry and Photophysics of Coordination Compounds
Photochemistry and Photophysics of Coordination Compounds
Photochemistry and Photophysics of Coordination Compounds
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Top Curr Chem (2007) 280: 37–67<br />
DOI 10.1007/128_2007_141<br />
© Springer-Verlag Berlin Heidelberg<br />
Published online: 11 July 2007<br />
<strong>Photochemistry</strong> <strong>and</strong> <strong>Photophysics</strong><br />
<strong>of</strong> <strong>Coordination</strong> <strong>Compounds</strong>: Chromium<br />
Noel A. P. Kane-Maguire<br />
Department <strong>of</strong> Chemistry, Furman University, 3300 Poinsett Highway,<br />
Greenville, SC 29613, USA<br />
noel.kane-maguire@furman.edu<br />
1 Introduction ................................... 38<br />
2 State Energy Levels <strong>and</strong> General Excited State Behavior ........... 38<br />
3 Ultrafast Dynamics <strong>of</strong> Cr(III) Lig<strong>and</strong> Field Excited States ......... 41<br />
3.1 Ultrafast Dynamics <strong>of</strong> 2 Eg State Formation in Cr(acac)3 ........... 42<br />
4 Photosubstitution Studies ........................... 43<br />
4.1 [Cr(phen)3] 3+ Photoracemization/Hydrolysis................. 43<br />
4.2 Axial Lig<strong>and</strong> Photodissociation in Cr(III) Porphyrins ............ 45<br />
5 Thermally Activated 2 Eg Excited State Relaxation Studies<br />
<strong>of</strong> Sterically Constrained Systems ....................... 47<br />
5.1 [Cr(sen)] 3+ <strong>and</strong> [Cr[18]aneN6] 3+ ....................... 49<br />
5.1.1 [Cr(sen)3] 3+ ................................... 49<br />
5.1.2 [Cr[18]aneN6] 3+ ................................. 50<br />
5.2 trans-[Cr(N4)(CN)2] +<br />
(where N4 = cyclam, 1,11-C3-cyclam, <strong>and</strong> 1,4-C2-cyclam).......... 51<br />
6 Energy Transfer Studies ............................ 52<br />
6.1 Self-Exchange Energy Transfer Between Identical Chromophores . . . . . . 53<br />
7 Photoredox Behavior <strong>of</strong> [Cr(diimine)3] 3+ Systems .............. 54<br />
7.1 DNAInteractions ................................ 56<br />
8 Photoredox Involving Coordinated Lig<strong>and</strong>s ................. 59<br />
8.1 Photolabilization <strong>of</strong> NO from Cr(III)-Coordinated Nitrite . . . ....... 59<br />
8.2 Photogeneration <strong>of</strong> Nitrido Complexes from Cr(III) Coordinated Azide . . 61<br />
9 Final Comments ................................. 62<br />
References ....................................... 63<br />
Abstract The study <strong>of</strong> the photochemistry <strong>and</strong> photophysics <strong>of</strong> octahedral <strong>and</strong> pseudooctahedral<br />
Cr(III) complexes has a rich history. An initial discussion is devoted to<br />
a general appraisal <strong>of</strong> the state <strong>of</strong> these two subjects up to December 1998, after providing<br />
a framework <strong>of</strong> state energy levels <strong>and</strong> radiative <strong>and</strong> non-radiative relaxation processes<br />
relevant to Cr(III) systems. The remaining sections cover some <strong>of</strong> the more active areas<br />
in the Cr(III) field, such as ultrafast dynamics, photosubstitution, thermally activated
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