Abstract
Reaction of [Rh 2(O 2CC(CH 3) 3) 4] with cis-1,2-dicyano-1,2-bis(2,4,5-trimethyl-3-thienyl)ethene ( cis-dbe) or closed-dbe in benzene and dichloromethane yielded three novel Rh(II) complexes. Their structures were characterized and photochromic properties were studied. X-ray crystallographic analyses revealed that the coordination environments of the three metal complexes are quite different. Complex 2 exhibits a 1-D infinite chain structure with two cyano groups of the ligand bridging two metal ions while in complexes 1 and 3 the metal ions have a direct interaction with at least one of the sulfur atoms of the two bisthienylethene molecules. Closed-dbe of complex 3 was transferred to the ring-open form in the crystalline phase upon photoexcitation with 529 nm light. It underwent a photocycloreversion reaction although the metal atom is coordinated to the thienyl group. The irreversible cyclization reaction was presumably attributed to the fixed rotation of thienyl rings, short Rh S distance and steric hindrance of anions.
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