Synthetic Model for FRET Constructed from Covalently Linked Porphyrin Dimers through a Pyrene Bridge

Abstract

We report the synthesis and characterization of two porphyrin arrays C 6 F 5 -PyZnDP and Mes-PyZnDP covalently linked by a pyrene moiety which differs from their substituents at their meso-positions. The key precursor bis-dipyrromethane linked with a pyrene bridge was prepared by the acidcatalyzed condensation of pyrene-1,6-dialdehyde with excess pyrrole. The synthesis of C 6 F 5 -PyZnDP was carried out via two different synthetic routes, with one being efficient over the other. Therefore, the superior route was employed for the synthesis of C 6 F 5 -PyZnDP and Mes-PyZnDP. Both the free base and metalated diporphyrins show bathochromically shifted absorption and intense red emission due to the extended π-conjugation through pyrene and porphyrins. The single-crystal X-ray structure reveals an orthogonal orientation of pyrene in between the two planar porphyrins and a slipped stacked packing arrangement in the crystal structure with large meso−meso distances. DFT analysis of both the ground state and the excited S1 state of the macrocycles indicates the difference in the HOMO and LUMO contribution in both the states arising from slight twisting from the mean orthogonal position in the excited state. Further, the Forster energy transfer (FRET) efficiencies from pyrene (donor) to the covalently linked Zn-porphyrins (acceptor) are estimated to be 85 and 91% for Mes-PyZnDP and C 6 F 5 -PyZnDP, respectively.