Synthesis of non-covalent BODIPY-metalloporphyrin dyads and triads

Abstract

Boron-dipyrromethenes (BODIPY) containing oxypyridine substituents at 3- and 3,5-positions and metalloporphyrins (Zn(II), Ru(II)) were used to synthesize four non-covalent BODIPY–metalloporphyrin dyads and four BODIPY–metalloporphyrin triads assembled using metal–pyridine ‘N’ interaction. The formation of BODIPY–metalloporphyrin assemblies was confirmed by 1D and 2D NMR methods and X-ray crystal structure obtained for one of the BODIPY–metalloporphyrin dyad. In 1H NMR, the signals of oxypyridine group(s) of BODIPY unit showed significant upfield shifts supporting the coordination of oxypyridine group of BODIPY unit to metalloporphyrin unit. The NMR study also indicated that Zn(II) porphyrin forms relatively weak BODIPY–Zn(II) porphyrin conjugates, whereas Ru(II) porphyrin forms strong BODIPY–Ru(II) porphyrin conjugates. The X-ray structure solved for BODIPY–Zn(II)porphyrin dyad revealed that the Zn(II) porphyrin coordinated to the BODIPY unit obliquely and the angle between the Zn(II) porphyrin and the pyridyl ring is 70°. The absorption properties of stable BODIPY–Ru(II) porphyrin conjugates showed the overlapping absorption features of both the components and the fluorescence studies indicated that the BODIPY unit emission was significantly quenched on coordination with RuTPP(CO) unit. The electrochemical studies exhibited the features of both BODIPY and metalloporphyrin units in dyads and traids.