Synthesis and Properties of Nonaromatic meso-fused Heterobenzihomoporphyrin(2.1.1.1)s.

Fluorene-based tripyrrane has been used as a fused precursor to synthesize three novel examples of nonaromatic meso-fused thia and selenabenzihomoporphyrin(2.1.1.1)s by condensing it with appropriate 2,5-bis(hydroxymethyl)aryl thiophene or selenophene under acid catalyzed conditions. The meso-fused heterobenzihomoporphyrins contain one fluorene unit, two pyrrole rings and one thiophene/selenophene ring connected via five meso-carbons in the macrocyclic framework. The macrocycles were thoroughly characterized by HR-MS, 1D and 2D NMR, absorption, cyclic voltammetry and DFT/TD-DFT studies. NMR, absorption, and DFT studies indicated the nonaromatic nature of meso-fused heterobenzihomoporphyrins. The macrocycles displayed one intense band at ∼380 nm along with a shoulder band at 450 nm and a broad band in the region of 590-850 nm which were bathochromically shifted in the monoprotonated derivatives and absorbed prominently in the NIR region with the peak maxima at ∼1035 nm. The electrochemical studies revealed that the macrocycles showed three well-defined oxidations and reductions, and TD-DFT studies corroborated experimental observations.