Core-modified isophlorin-metal complexes were successfully prepared by redox-coupled complexation of P,S,N2-hybrid porphyrin with zerovalent palladium, nickel, and platinum. In this transformation, the core-phosphorus atom plays crucial roles in enhancing the electron-accepting ability of the 18π porphyrin ring and stabilizing the 20π isophlorin ring owing to high P-M affinity. The isolated Pd and Pt complexes are chemically stable under ambient conditions. The Pd-P,S,N2 isophlorin complex was structurally characterized by X-ray crystallography, which revealed a distorted 20π plane with a square planar palladium(II) center. Experimental (1H, UV-vis, and X-ray) and theoretical (density functional theory calculations) results suggest that the P,S,N2-isophlorin-metal complexes possess nonaromaticity in terms of both magnetic and geometrical criteria.
All Science Journal Classification (ASJC) codes
- 化学 (全般)