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

We report the synthesis and characterization of two porphyrin arrays C6F5-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 acid catalyzed condensation of pyrene-1,6-dialdehyde with excess pyrrole. The synthesis of C6F5-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 C6F5-PyZnDP and Mes-PyZnDP. Both the free base and metalated diporphyrins show bathochromically shifted absorption and intense red emission due to the extended pi-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 Fo''rster 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 C6F5-PyZnDP, respectively.

Automated summary

We synthesized and characterized two porphyrin arrays, C6F5-PyZnDP and Mes-PyZnDP, linked by a pyrene moiety with different substituents at their meso-positions. The key precursor bis-dipyrromethane linked with a pyrene bridge was prepared. C6F5-PyZnDP was synthesized through two different routes, with one being more efficient, and both the free base and metalated diporphyrins showed bathochromically shifted absorption and intense red emission.