Abstract
[Cu(SRaaiNR′)(PPh 3)X] complexes are synthesized by the reaction of CuX (X = Cl, Br, I), triphenylphosphine and 1-alkyl-2-[( o-thioalkyl)phenylazo]imidazole (SRaaiNR′). The single crystal X-ray structure of [Cu(SEtaaiNH)(PPh 3)I] (SEtaaiNH = 2-[( o-thioethyl)phenylazo]imidazole) shows a distorted tetrahedral geometry of the copper center with bidentate, N(azo), N(imidazole) chelation of SEtaaiNH and coordination from PPh 3 and iodine. These complexes show a trans-to- cis isomerization upon irradiation with UV light. The reverse transformation, c is-to- trans isomerization, is very slow with visible light irradiation and is thermally accessible. The quantum yields ( ϕ t→c) of the trans-to- cis isomerization of [Cu(SRaaiNR′)(PPh 3)X] are lower than the free ligand values. This is due to the increased mass and rotor volume of the complexes compared to the free ligand data. The rate of isomerization follows the order: [Cu(SRaaiNR′)(PPh 3)Cl] < [Cu(SRaaiNR′)(PPh 3)Br] < [Cu(SRaaiNR′)(PPh 3)I]. The activation energy ( E a) of the cis-to- trans isomerization is calculated by a controlled temperature reaction. DFT computation of representative complexes has been used to determine the composition and energy of the molecular levels.
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