Unsymmetric Pentacene- and Pentacenequinone-Fused Porphyrins: Understanding the Effect of Cross- and Linear-Conjugation.

Unsymmetric pentacenequinone-fused (cross-conjugated) and pentacene-fused (linear-conjugated) porphyrins were designed and synthesized. The cross-conjugated ( - ) and linear-conjugated ( - ) porphyrins displayed strikingly different sets of optical and electronic properties, both of which are unusual and nontypical of porphyrins. MCD, DFT, and TDDFT calculations suggest that multiple charge transfer states exist in both π-conjugated systems, which contributes to the complex absorption and MCD spectra of these molecular systems. The general Gouterman's four-orbital model used to explain porphyrin spectroscopy led to contradicting theoretical and experimental data, and is thus not applicable for these molecular systems. The "2 + 4" and "3 + 3" active spaces have been deduced and have proven effective to interpret the absorption and MCD spectra of the pentacenequinone-fused (cross-conjugated) and pentacene-fused (linear-conjugated) porphyrins, respectively. Spectroelectrochemistry of - revealed broad and intense IR absorptions in the range of 1500-2500 nm, illustrating the exceptional ability of these pentacene-fused systems to accommodate positive charges. A pronounced metal effect was observed for pentacene-fused porphyrins. While pentacene-fused Ni(II) porphyrin ( ) demonstrated an abnormal ability to stabilize pentacene with a half-life of >28.3 days, the half-life of the free base and Zn(II) counterparts were normal, similar to those of pentacene analogues. This work provides important and useful information on guiding new material designs.