期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 31, 页码 13063-13070出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202004867
关键词
calix[n]phyrins; cyclic BODIPY; exciton coupling; NIR dyes; porphyrinoids
资金
- Shanghai University
- National Natural Science Foundation of China [21901155]
- Eastern Scholars program from the Shanghai Municipal Education Committee
- National Research Foundation of Korea (NRF) - South Korean government (MEST) [2016R1E1A1A01943379]
- National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) [KSC-2019-CRE-0201]
- U.S. National Science Foundation [CHE-1807152]
- Robert A. Welch Foundation [F-0018]
- National Research Foundation of Korea [2016R1E1A1A01943379] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
Two giant calix[n]phyrin derivatives namely calix[8]- (4) and calix[16]phyrin (5), involving two and four BF2 units, respectively, were prepared through the condensation of the bis-naphthobipyrrolylmethene-BF2 complex (3) with pentafluorobenzaldehyde. Calix[n]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82x10(5) m(-1) cm(-1), 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.
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