Zhu He, Chen Qiang, Rončević Igor, Christensen Kirsten E, Anderson Harry L
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, OX1 3TA, Oxford, UK.
Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Prague, Czech Republic.
Angew Chem Int Ed Engl. 2023 Aug 1;62(31):e202307035. doi: 10.1002/anie.202307035. Epub 2023 Jun 23.
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.
π共轭纳米带因其独特的电子结构和电荷传输行为而备受关注。在此，我们报道了一系列完全边缘融合的卟啉 - 蒽低聚带（二聚体和三聚体）的合成，以及对相应无限聚合物的计算研究。卟啉二聚体和三聚体通过单链前体的氧化环脱氢反应，使用2,3 - 二氯 - 5,6 - 二氰基 - 1,4 - 苯醌（DDQ）和三氟甲磺酸（TfOH）以高产率合成。二聚体的晶体结构表明，中心π体系是平的，每个卟啉末端有轻微的S形波畸变。扩展的π共轭导致吸收光谱发生显著红移：融合二聚体和三聚体的吸收最大值分别出现在1188 nm和1642 nm处（对于溶解在甲苯中的镍配合物）。使用对甲苯基溴化镁将二聚体中的配位金属从Ni变为Mg，从而得到游离碱和Zn配合物。这些结果为具有集成金属卟啉单元的更长π共轭纳米带开辟了一条通用途径。
