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  • Title: trans-Dichloro-bis-(arylazoimidazole)palladium(II): synthesis, structure, photoisomerization, and DFT calculation.
    Author: Pratihar P, Mondal TK, Patra AK, Sinha C.
    Journal: Inorg Chem; 2009 Apr 06; 48(7):2760-9. PubMed ID: 19253980.
    Abstract:
    Reaction between PdCl(2) and 1-alkyl-2-(arylazo)imidazole (RaaiR') or 1-alkyl-2-(naphthyl-alpha/beta-azo)imidazole (alpha/beta-NaiR') under reflux in ethanol has isolated complexes of compositions Pd(RaaiR')(2)Cl(2) (5, 6) and Pd(alpha/beta-NaiR')(2)Cl(2) (7, 8). The X-ray structure determination of one of the molecules, Pd(alpha-NaiBz)(2)Cl(2) (7c), has reported a trans-PdCl(2) configuration, and alpha-NaiBz acts as monodentate N(imidazole) donor ligand. The spectral (IR, UV-vis, (1)H NMR) data support the structure. UV light irradiation (light source: Perkin-Elmer LS 55 spectrofluorimeter, Xenon discharge lamp, lambda = 360-396 nm) in a MeCN solution of the complexes shows E-to-Z isomerization of the coordinated azoimidazole unit. The reverse transformation, Z-to-E, is very slow with visible light irradiation. Quantum yields (phi(E-->Z)) of E-to-Z isomerization are calculated, and phi is lower than that of the free ligand but comparable with those of Cd(II) and Hg(II) complexes of the same ligand. The Z-to-E isomerization is a thermally induced process. The activation energy (E(a)) of Z-to-E isomerization is calculated by controlled-temperature experimentation. cis-Pd(azoimidazole)Cl(2) complexes (azomidazole acts as N(imidazole) and N(azo) chelating ligand) do not respond upon light irradiation, which supports the idea that the presence of noncoordinated azo-N to make free azo (-N=N-) function is important to reveal photochromic activity. DFT calculation of Pd(alpha-NaiBz)(2)Cl(2) (7c) has suggested that the HOMO of the molecule is constituted of Pd (32%) and Cl (66%), and hence photo excitation may use the energy of Pd and Cl instead of that of the photofunctional -N=N-Ar motif; thus, the rate of photoisomerization and quantum yield decrease versus the free ligand values.
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