The structure and photophysics of di-iodo-zinc(II) complexes of long alkyl chain substituted imidazolyl motif of arylazoimidazoles and the DFT computation.

Distorted tetrahedral structure of [Zn(Haai-C10H21)2I2] (Haai-C10H21, 1-decayl-2-(arylazo)imidazole) has been supported by single crystal X-ray diffraction study. The structures of other complexes, [Zn(Raai-CnH2n+1)2I2] (n=10, 12, 14, 16, 18, 20, 22) have been determined by spectroscopic data (FT-IR, UV-vis, (1)H NMR). The complexes show light induced photoisomerisation, E-to-Z (trans-to-cis) of coordinated, Raai-CnH2n+1. The Z-to-E (cis-to-trans) isomerisation is also carried out by thermal activation route. The quantum yields of the E→Z progression (ϕE→Z) of the complexes are less than that of free ligand, which could be due to increase in molar mass and molar volume of the complexes than that of free ligands. The activation energy (Ea) of Z→E isomerisation of the complexes is is less than that of free ligands. This observation is also consistent with femtosecond transient absorption results which suggests that the E(trans)→Z(cis) isomerization occurs through the motion of pendant NNAr of the molecule. The temporal profiles of free ligand shows three decay processes corresponds to 0.24ps (S2 state) and subsequent decay, 0.85ps of the S1 state and finally 5ps to the hot ground state at 500nm. The complexes also show three decay periods approximately at 0.25ps, 1.3ps and 13ps. The spectral property and photochromic efficiency have been explained by DFT computation of optimized geometry of the complexes.