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Abstract A series of largely π‐extended multichromophoric molecules including cross‐conjugated, half cross‐conjugated, conjugation‐interrupted and linearly conjugated systems were synthesized and characterized. These multichromophoric molecular systems revealed interesting structural‐property relationships. Bisporphyrin‐fused pentacenesPen‐1 bandPen‐2 ashowed rich redox chemistry with 7 and 8 observable redox states, respectively. The linearly‐conjugated bisporphyrin‐fused pentacenes (Pen‐1 bandPen‐2 a) possess much narrower HOMO–LUMO gaps (1.65 and 1.42 eV redox, respectively) and higher HOMO energy levels than those of their pentacene analogues (2.23 and 2.01 eV redox, respectively), similar to those of much less stable hexacenes and heptacenes. An estimated half‐life of >945 h was obtained for bisporphyrin‐fused pentacenePen‐2 a, which is much longer than that of its pentacene analogue (BPE‐P, half‐life, 33 h).more » « less
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Abstract A series of largely π‐extended multichromophoric molecules including cross‐conjugated, half cross‐conjugated, conjugation‐interrupted and linearly conjugated systems were synthesized and characterized. These multichromophoric molecular systems revealed interesting structural‐property relationships. Bisporphyrin‐fused pentacenesPen‐1 bandPen‐2 ashowed rich redox chemistry with 7 and 8 observable redox states, respectively. The linearly‐conjugated bisporphyrin‐fused pentacenes (Pen‐1 bandPen‐2 a) possess much narrower HOMO–LUMO gaps (1.65 and 1.42 eV redox, respectively) and higher HOMO energy levels than those of their pentacene analogues (2.23 and 2.01 eV redox, respectively), similar to those of much less stable hexacenes and heptacenes. An estimated half‐life of >945 h was obtained for bisporphyrin‐fused pentacenePen‐2 a, which is much longer than that of its pentacene analogue (BPE‐P, half‐life, 33 h).more » « less
