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Abstract: Reaction of Cu(ClO4)2·6H2O, SRaaiNR′ (1-alkyl-2-[(o-thioalkyl)phenylazo]imidazole) and NH4SCN (1:1:2mol ratio) affords distorted square pyramidal, [CuII(SRaaiNR′)(SCN)2] (3) compound while identical reaction with [Cu(MeCN)4](ClO4) yields –SCN– bridged coordination polymer, [CuI(SRaaiNR′)(SCN)] n (4). These two redox states [CuII and CuI] are interconvertible; reduction of [CuII(SRaaiNR′)(SCN)2] by ascorbic acid yields [CuI(SRaaiNR′)(SCN)] n while the oxidation of [CuI(SRaaiNR′)(SCN)] n by H2O2 in presence of excess NH4SCN affords [CuII(SRaaiNR′)(SCN)2]. They are structurally confirmed by single crystal X-ray diffraction study. Cyclic voltammogram of the complexes show Cu(II)/Cu(I) redox couple at ∼0.4V and azo reductions at negative to SCE. UV light irradiation in MeCN solution of [CuI(SRaaiNR′)(SCN)] n (4) show trans-to-cis isomerisation of coordinated azoimidazole. The reverse transformation, cis-to-trans, is very slow with visible light irradiation while the process is thermally accessible. Quantum yields (ϕ t→c) of trans-to-cis isomerisation are calculated and free ligands show higher ϕ than their Cu(I) complexes. The activation energy (E a) of cis-to-trans isomerisation is calculated by controlled temperature experiment. Copper(II) complexes, 3, do not show photochromism. DFT and TDDFT calculation of representative complexes have been used to determine the composition and energy of molecular levels and results have been used to explain the solution spectra, photochromism and redox properties of the complexes. [ABSTRACT FROM AUTHOR]

Abstract: The reaction of Pd(β-NaiR)Cl2 (2) [β-NaiR (1)=1-alkyl-2-(naphthyl-β-azo)imidazoles] with ArNH2 in MeCN has yielded a C–N coupled product chloro[1-alkyl-2-{(7-imidoaryl)naphthyl-β-azo}imidazole-N,N′,N′′]palladium(II), Pd(β-NaiR–N–Ar)Cl (3–5) and coupling takes place at ortho-C–H position of pendant naphthyl group. The structural confirmation has been achieved by single crystal X-ray structure determination of the representative complexes, Pd(β-NaiEt)Cl2 (2b) and Pd(β-NaiEt–N–C6H4–Cl-p)Cl (5b). The electronic spectra of the products, 3–5, exhibit characteristic transition within 600–900nm those are absent in Pd(β-NaiR)Cl2 (2). Cyclic voltammogram shows one oxidative response and two ligand reductions. The products are emissive. The excited state decays via radiative and non-radiative biexponential routes. The electronic structure, spectra and redox properties are explained by DFT computation. [Copyright &y& Elsevier]