Bistable Photochromic Organometallics Based on Linkage Isomerization: Photochemistry of Dicarbonyl(5-methylcyclopentadienyl
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- 作者：Tung T. To ; Craig E. Barnes ; and Theodore J. Burkey
- 刊名：Organometallics
- 出版年：2004
- 出版时间：May 24, 2004
- 年：2004
- 卷：23
- 期：11
- 页码：2708 - 2714
- 全文大小：117K
- 年卷期：v.23,no.11(May 24, 2004)
- ISSN：1520-6041
文摘
Cyclopentadienylmanganese complexes of the general formula (
5-C5H4CH3)Mn(CO)2L,where L is a nonchelatable, bifunctional ligand, were found to be photochromic. Irradiationof (5-C5H4CH3)Mn(CO)2L(3-cyanomethylpyridine) with alternating visible and UV lightproduced alternating yellow and red solutions, and fatigue of this response was inhibitedwhen free 3-(cyanomethyl)pyridine was present during irradiation. Similar results wereobserved when L is pyridine in the presence of dispersed acetonitrile. Irradiation of (5-C5H4CH3)Mn(CO)3 and a pyridine derivative RC5H4N (R = 3-CH2CN, 2-CH2CN, 4-CHCHPh,4-CHCH2) generated (5-C5H4CH3)Mn(CO)2L in situ, which likewise showed a photochromicresponse. The results demonstrate that the linkage isomerization occurs by unimolecularand bimolecular processes and that linkage isomerization is an effective photochromicmechanism for organometallics.
5-C5H4CH3)Mn(CO)2L,where L is a nonchelatable, bifunctional ligand, were found to be photochromic. Irradiationof (5-C5H4CH3)Mn(CO)2L(3-cyanomethylpyridine) with alternating visible and UV lightproduced alternating yellow and red solutions, and fatigue of this response was inhibitedwhen free 3-(cyanomethyl)pyridine was present during irradiation. Similar results wereobserved when L is pyridine in the presence of dispersed acetonitrile. Irradiation of (5-C5H4CH3)Mn(CO)3 and a pyridine derivative RC5H4N (R = 3-CH2CN, 2-CH2CN, 4-CHCHPh,4-CHCH2) generated (5-C5H4CH3)Mn(CO)2L in situ, which likewise showed a photochromicresponse. The results demonstrate that the linkage isomerization occurs by unimolecularand bimolecular processes and that linkage isomerization is an effective photochromicmechanism for organometallics.