Excitonically Coupled Cyclic BF2 Arrays of Calix[8]- and Calix[16]phyrin as Near-IR-Chromophores

Taeyeon Kim, Zhiming Duan, Sangita Talukdar, Chuanhu Lei, Dongho Kim, Jonathan L. Sessler, Tridib Sarma

Research output: Contribution to journalArticle

Abstract

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 4.82×105 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.

Original languageEnglish
Pages (from-to)13163-13170
Number of pages8
JournalAngewandte Chemie
Volume132
Issue number31
DOIs
Publication statusPublished - 2020 Jul 27

All Science Journal Classification (ASJC) codes

  • Engineering(all)

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