Anthracene-Porphyrin Nanoribbons.
Anthracene-Porphyrin Nanoribbons.
复制标题
DOI：
10.1002/anie.202307035
复制
发表时间：
2023-06
影响因子：
--
通讯作者：
He Zhu;Qiang Chen;Igor Rončević;Kirsten E. Christensen;H. Anderson
中科院分区：
文献类型：
--
作者：
He Zhu;Qiang Chen;Igor Rončević;Kirsten E. Christensen;H. Anderson
π共轭纳米带由于其独特的电子结构和电荷输运行为而引起人们的兴趣。在这里，我们报告了一系列完全边缘稠合的卟啉-蒽低聚带（二聚体和三聚体）的合成，以及相应的无限聚合物的计算研究。以2，3-二氯-5，6-二氰基-1，4-苯醌（DDQ）和三氟甲磺酸（TfOH）为原料，通过氧化环化脱氢反应，高产率地合成了卟啉二聚体和三聚体。二聚体的晶体结构表明，中心π-系统是平坦的，在每个卟啉末端有轻微的S形波畸变。扩展的π-共轭导致吸收光谱的显著红移：融合的二聚体和三聚体的最大吸收分别出现在1188 nm和1642 nm处（对于溶解在甲苯中的镍络合物）。二聚体中的配位金属从Ni变为Mg，使用对甲苯基溴化镁，提供获得游离碱和Zn络合物的途径。这些结果为具有整合的金属卟啉单元的更长的π共轭纳米带开辟了一条通用的途径。
π-Conjugated nanoribbons attract interest because of their unusual electronic structures and charge-transport behavior. Here, we report the synthesis of a series of fully edge-fused porphyrin-anthracene oligomeric ribbons (dimer and trimer), together with a computational study of the corresponding infinite polymer. The porphyrin dimer and trimer were synthesized in high yield, via oxidative cyclodehydrogenation of singly linked precursors, using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH). The crystal structure of the dimer shows that the central π-system is flat, with a slight S-shaped wave distortion at each porphyrin terminal. The extended π-conjugation causes a dramatic red-shift in the absorption spectra: the absorption maxima of the fused dimer and trimer appear at 1188 nm and 1642 nm, respectively (for the nickel complexes dissolved in toluene). The coordinated metal in the dimer was changed from Ni to Mg, using p-tolylmagnesium bromide, providing access to free-base and Zn complexes. These results open a versatile avenue to longer π-conjugated nanoribbons with integrated metalloporphyrin units.