Synthesis of Doubly Strapped meso–meso‐Linked Porphyrin Arrays and Triply Linked Conjugated Porphyrin Tapes

Abstract 1,10‐Dioxydecamethylene doubly strapped Zn II ‐porphyrin S1 was prepared and treated with AgPF 6 to give meso – meso ‐linked porphyrin oligomers S n ( n = 2, 3, 4, 6, 8, and 12), which were converted to triply linked porphyrin tapes TS n by meso , meso′ ‐dibromo meso – meso ‐linked porphyrin arrays BS n and meso , meso′ ‐diphenyl meso – meso ‐linked porphyrin arrays PS n . The structures of S1 and S2 have been determined by single‐crystal X‐ray diffraction analysis. Characteristically, S n exhibit sharp Q(0,0) absorption and fluorescence bands. Low energy Q‐band‐like absorption bands of TS n are progressively red‐shifted with an increase in the number of porphyrins without saturation behavior of conjugation. The double straps suppress π–π stacking to some extent as seen from partial preservation of vibration structures in the Q‐band‐like bands of TS4 and TS6 and improve the chemical stabilities of longer tapes such as TS8 and TS12 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)