Synthesis, Crystal Structure, and Nonlinear Optical Behavior of β-Unsubstituted meso−meso E-Vinylene-Linked Porphyrin Dimers

A vinylene-linked porphyrin dimer, with no substituents at the β-positions, has been synthesized by CuI/CsF promoted Stille coupling. In the
crystal structure of this dimer, the C2H2 bridge is twisted by 45° relative to the plane of the porphyrins. The absorption, emission spectra, and
electrochemistry reveal substantial porphyrin−porphyrin π-conjugation. The triplet excited-state absorption spectrum of this dimer makes it
suitable for reverse saturable absorption at 710−900 nm.

通过CuI/CsF催化的Stille偶联反应成功合成了不含β位取代基的乙烯基连接的卟啉二聚体。在该二聚体的晶体结构中，C2H2桥相对于卟啉平面扭曲了45°。吸收光谱、发射光谱和电化学性质揭示了显著的卟啉-卟啉π共轭。该二聚体的三重激发态吸收光谱使其适用于710-900 nm范围内的反向饱和吸收。