Bistable Photochromic Organometallics Based on Linkage Isomerization: Photochemistry of Dicarbonyl(η<sup>5</sup>-methylcyclopentadienyl)manganese(I) Derivatives with a Bifunctional, Nonchelating Ligand
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Cyclopentadienylmanganese complexes of the general formula (η5-C5H4CH3)Mn(CO)2L, where L is a nonchelatable, bifunctional ligand, were found to be photochromic. Irradiation of (η5-C5H4CH3)Mn(CO)2L(3-cyanomethylpyridine) with alternating visible and UV light produced alternating yellow and red solutions, and fatigue of this response was inhibited when free 3-(cyanomethyl)pyridine was present during irradiation. Similar results were observed when L is pyridine in the presence of dispersed acetonitrile. Irradiation of (η5-C5H4CH3)Mn(CO)3 and a pyridine derivative RC5H4N (R = 3-CH2CN, 2-CH2CN, 4-CHCHPh, 4-CHCH2) generated (η5-C5H4CH3)Mn(CO)2L in situ, which likewise showed a photochromic response. The results demonstrate that the linkage isomerization occurs by unimolecular and bimolecular processes and that linkage isomerization is an effective photochromic mechanism for organometallics.
