Fully Conjugated Porphyrin Tapes with Electronic Absorption Bands That Reach into Infrared

Abstract
Scandium(III)-catalyzed oxidation ofmeso-meso–linked zinc(II)-porphyrin arrays (up to dodecamers) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) led to efficient formation of triply meso-meso–, β-β–, and β-β–linked zinc(II)-oligoiporphyrins with 62 to 91% yields. These fused tape-shaped porphyrin arrays display extremely red-shifted absorption bands that reflect extensively π-conjugated electronic systems and a low excitation gap. The lowest electronic absorption bands become increasingly intensified and red-shifted upon the increase in the number of porphyrins and eventually reach a peak electronic excitation for the dodecamer at ∼3500 wavenumber. The one-electron oxidation potentials also decreased progressively upon the increase in the number of porphyrins. These properties in long and rigid molecular shapes suggest their potential use as molecular wires.

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