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Excitonically Coupled Cyclic BF 2 Arrays of Calix[8]‐ and Calix[16]phyrin as Near‐IR‐Chromophores
Author(s) -
Kim Taeyeon,
Duan Zhiming,
Talukdar Sangita,
Lei Chuanhu,
Kim Dongho,
Sessler Jonathan L.,
Sarma Tridib
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202004867
Subject(s) - chromophore , exciton , fluorescence , coupling (piping) , absorption (acoustics) , condensation , extinction (optical mineralogy) , materials science , crystallography , photochemistry , chemistry , optics , condensed matter physics , physics , mineralogy , thermodynamics , metallurgy , composite material
Two giant calix[ n ]phyrin derivatives namely calix[8]‐ ( 4 ) and calix[16]phyrin ( 5 ), involving two and four BF 2 units, respectively, were prepared through the condensation of the bis‐naphthobipyrrolylmethene‐BF 2 complex ( 3 ) with pentafluorobenzaldehyde. Calix[ n ]phyrins 4 and 5 display extremely high extinction coefficients (3.67 and 4.82×10 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.