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The synthesis, characterization and photoswitching behavior of a new salen type Schiff base N,N'-bis(2-hydroxy-5-phenylazobenzilidene)-2,4,6-trimethylbenzene-1,3-diamine (H₂L) and a binuclear zinc(ii) metallacycle [{Zn(L)}2·2H2O] (1) have been described. Both H₂L and 1 have been characterized by satisfactory elemental analyses, spectral (FT-IR, (1)H, (13)C NMR, ESI-MS, electronic absorption, emission) and electrochemical studies. Crystal structures of both H₂L and 1 have been authenticated by single crystal X-ray diffraction analyses. These exhibit trans-cis photoisomerization upon exposure to UV light (365 nm) and get back to a more stable trans-form after withdrawal of the light. Electronic absorption, emission, (1)H NMR and cyclic voltammetric studies revealed that trans-cis isomerization in metallacycle 1 is rather rapid (~5.0 s) relative to H₂L (~25 s) which has been supported by theoretical studies (DFT). Relatively fast photoisomerization in 1 compared to H₂L is facilitated by a small energy gap between HOMO levels of the trans- and cis-isomers. The percentage trans-cis conversion ratio for both H₂L and 1 has been evaluated (55-45, H₂L; 60-40%, 1) by (1)H NMR studies.

A novel C-C coupled 1D-polymeric chain (1) is obtained by reaction of HgCl2 and hmp-H (2-(2-hydroxymethyl pyridine)) (1 : 1) in MeOH at ambient temperature. However, a new class of μ-oxo and μ-chloro bridged polymers (2) has been obtained by altering the metal : ligand ratio to 1 : 2.