Department of Chemistry and Spectroscopy Laboratory for Functional π-Electronic Systems, Yonsei University, Seoul, 03722, Korea.
Center for Supramolecular Chemistry and Catalysis and Department of Chemistry, College of Science, Shanghai University, Shanghai, 200444, P. R. China.
Angew Chem Int Ed Engl. 2020 Jul 27;59(31):13063-13070. doi: 10.1002/anie.202004867. Epub 2020 May 28.
Two giant calix[n]phyrin derivatives namely calix[8]- (4) and calix[16]phyrin (5), involving two and four BF units, respectively, were prepared through the condensation of the bis-naphthobipyrrolylmethene-BF complex (3) with pentafluorobenzaldehyde. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82×10 m cm , respectively) in the near-IR region, which was taken as initial evidence for strong excitonic coupling within these cyclic multi-chromophoric systems. Detailed insights into the effect of excitonic coupling dynamics on the electronic structure and photophysical properties of the macrocycles came from fluorescence, time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements. Support for these experimental findings came from theoretical studies. Theory and experiment confirmed that the coupling between the excitons depends on the specifics of the calix[n]phyrin structure, not just its size.
两个巨型杯[环]芳烃衍生物，即杯[8]-（4）和杯[16]卟啉（5），分别涉及两个和四个 BF 单元，是通过双萘并[B]吡咯-亚甲基-BF 配合物（3）与五氟苯甲醛缩合制备的。杯[环]芳烃 4 和 5 在近红外区域具有极高的消光系数（分别为 3.67 和 4.82×10 m cm ），这被视为这些环状多生色团体系中强激子耦合的初步证据。荧光、时间相关单光子计数（TCSPC）和瞬态吸收（TA）测量深入了解了激子耦合动力学对大环电子结构和光物理性质的影响。理论研究为这些实验结果提供了支持。理论和实验证实，激子之间的耦合取决于杯[环]芳烃结构的具体情况，而不仅仅是其大小。
