Abstract
Abstract The photophysical behavior of a series of flexible di-2-pyridylaminomethyl substituted ligands systematically substituted on a rigid benzene core and their corresponding mono-metallic Re(I) complexes have been investigated by steady state and time-resolved fluorescence spectroscopy in different composition of DMSO–water binary solvent mixtures. Unusual fluorescence properties in lower DMSO content ( X DMSO = 0.1–0.3) solvent mixtures is consistent with fascinating property of DMSO, which is known to perturb the hydrogen bonding ability of water with the solute. Spin allowed inter-ligand π–π * transition is more apparent in (1, 3) substituted systems. The calculated spectroscopic parameters of the complexes are significantly different from the ligands, mainly due to ligand to metal charge transfer. The experimental observations are in very good agreement with the theoretical results obtained at B3LYP/6-31G(d,p)/LANL2DZ level of density functional theory (DFT) calculation. Natural bond orbital (NBO) analysis and examination of frontier molecular orbitals reveal that the basic architecture of the symmetrically substituted multi-chromophoric ligand can induce excitation energy hopping, similar to an artificial antenna system.
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