Metalloporphyrins substituted with N-carbazolyl groups quadruply at meso positions

Abstract

As a new family of porphyrinoids with broad absorption bands that efficiently harvest sunlight, the metal complexes of a porphyrin quadruply substituted with [Formula: see text]-carbazolyl groups at the meso positions were photometrically and structurally characterized. The porphyrins exhibited characteristic broad bands in the range of 450–500 nm, due to the charge transfer band from carbazole to porphyrin. Ligand exchange at the axial position of the zinc complex with an aquo ligand affected the absorption spectrum, and a hyper-hypsochromic shift of the broad band was observed by the coordination of methanol. Furthermore, the lowest unoccupied molecular orbital (LUMO) levels of the metalloporphyrins were lowered by the electron-withdrawing effect of the perpendicularly oriented carbazolyl groups. In the solid state, zinc-porphyrin was self-assembled into a one-dimensional coordination polymer by intermolecular axial coordination.