A series of porphyrin dimers bridged by one or two rigid arylenedioxy linkers was successfully synthesized by catalyst‐free meso‐aryloxylation involving nucleophilic aromatic substitution. The orientational freedom and conformation of the two porphyrin macrocycles in the mono‐bridged dimers depended on the steric hindrance between the macrocycles and substituents on the arylenedioxy linkers. On the other hand, the bis‐bridged dimers exhibited a highly rigid cofacial conformation with a distinct interplanar distance. The fluorescence quantum yields of the bis‐bridged dimers (Φfl = 0.094 and 0.096) were quite similar to those of the monomers (Φfl = 0.13). Owing to their high rigidities, the nonradiative deactivation of the photoexcited states associated with dimerization, which are observed for reported dimers, are mostly suppressed, suggesting that those dimers have highest rigidities among the cofacial porphyrin dimers exploring emission properties. Cyclic voltammetry revealed the electronic communication between the porphyrin macrocycles in the closely stacked bis‐bridged dimer.

中文翻译：

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不含催化剂的亲核芳香取代基可高效合成亚芳基二氧基桥连的卟啉二聚体

通过涉及亲核芳族取代的无催化剂介孔芳氧基化反应成功合成了由一个或两个刚性亚芳基二氧基连接基桥接的一系列卟啉二聚体。单桥二聚体中两个卟啉大环的取向自由度和构象取决于大环与亚芳基二氧基连接基上的取代基之间的空间位阻。另一方面，双桥二聚体表现出高度刚性的界面构象，且具有明显的晶面间距。双桥二聚体的荧光量子产率（Φfl= 0.094和0.096）与单体的荧光量子产率（Φfl= 0.13）非常相似。由于它们的高刚性，与二聚化有关的光激发态的非辐射失活（据报道的二聚体观察到）被大部分抑制，这表明在研究发射特性的表面卟啉二聚体中，这些二聚体具有最高的刚性。循环伏安法揭示了紧密堆积的双桥二聚体中卟啉大环之间的电子通讯。