A 1,5-Naphthyridine-Fused Porphyrin Dimer: Intense NIR Absorption and Facile Redox Interconversion with Its Reduced Congener.

Pt -catalyzed cyclization of β-to-β ethynylene-bridged meso-amino Ni porphyrin dimer 4 followed by oxidation with PbO afforded 1,5-naphthyridine-fused porphyrin dimer 5 in good yield. This dimer possesses a redox-active 1,4-diazabutadiene linkage that is interconvertible with its reduced 1,2-diaminoethene linkage upon treatments with NaBH or PbO . The dimer 5 exhibits an intense NIR absorption and a narrow HOMO-LUMO gap with a remarkably low reduction potential mainly due to effective bonding interactions in the LUMO through the 1,4-diazabutadiene linkage. In contrast, the reduced dimer 7 is fairly electron-rich with high HOMO energy and shows a relatively large HOMO-LUMO gap compared to that of 5.