Abstract
Abstract The lowest excited triplet (T1) state of 3,3′-biisoquinoline(dicyano)platinum(II), [Pt(CN)2(i-biq)] was examined by time-resolved electron paramagnetic resonance (TREPR) and optical techniques in comparison with that of a ligand 3,3′-biisoquinoline (i-biq). Trans and cis i-biqs were assigned from obtained and calculated zero-field splittings (zfs') in the T1 state. The zfs parameter D increased with complex formation from 2.66 to 4.66 GHz in a rigid dimethylformamide solution; the polarization pattern of the spectrum was very different between the ligand and the complex. The triplet lifetime (ca. 1 s) of i-biq is also remarkably shortened in the complex (ca. 2 ms). These facts were analyzed in terms of the spin-orbit coupling (soc) between T1 (ππ*) and 1,3dπ*. From the analyses, the soc matrix element and the magnitude of delocalization of π* electrons over the Pt atom are obtained as 65 cm-1 and 0.02, respectively. The solvent dependences of the D value and the triplet lifetime also support the importance of the 1,3dπ* states for the T1 (ππ*) properties of the complex.
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