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

doi:10.1002/anie.202004867

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

17 Citations (Scopus)

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 language	English
Pages (from-to)	13063-13070
Number of pages	8
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	31
DOIs	https://doi.org/10.1002/anie.202004867
Publication status	Published - 2020 Jul 27

Bibliographical note

Funding Information:
The work in Shanghai was supported by Shanghai University, the National Natural Science Foundation of China (no. 21901155 to C. L.), and the Eastern Scholars program from the Shanghai Municipal Education Committee (to C.L.). The work at Yonsei University was supported by the National Research Foundation of Korea (NRF) through a grant funded by the South Korean government (MEST) (No. 2016R1E1A1A01943379 to D.K.). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with needed supercomputing resources, including technical support (KSC‐2019‐CRE‐0201). The work in Austin was supported by the U.S. National Science Foundation (CHE‐1807152 to J.L.S.) and the Robert A. Welch Foundation (F‐0018 to J.L.S.). We thank the staff of Beamline BL17B1 at the National Facility for Protein Science Shanghai and the Shanghai Synchrotron Radiation Facility for assistance during the single crystal X‐ray data collection. We thank Ms. Yanfei Niu and Prof. Xiaoli Zhao at East China Normal University for collecting the X‐ray data for compound . 3

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.202004867

Cite this

@article{5b4fa38df1864e33abb0f8169c28d926,

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

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.",

author = "Taeyeon Kim and Zhiming Duan and Sangita Talukdar and Chuanhu Lei and Dongho Kim and Sessler, {Jonathan L.} and Tridib Sarma",

note = "Funding Information: The work in Shanghai was supported by Shanghai University, the National Natural Science Foundation of China (no. 21901155 to C. L.), and the Eastern Scholars program from the Shanghai Municipal Education Committee (to C.L.). The work at Yonsei University was supported by the National Research Foundation of Korea (NRF) through a grant funded by the South Korean government (MEST) (No. 2016R1E1A1A01943379 to D.K.). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with needed supercomputing resources, including technical support (KSC‐2019‐CRE‐0201). The work in Austin was supported by the U.S. National Science Foundation (CHE‐1807152 to J.L.S.) and the Robert A. Welch Foundation (F‐0018 to J.L.S.). We thank the staff of Beamline BL17B1 at the National Facility for Protein Science Shanghai and the Shanghai Synchrotron Radiation Facility for assistance during the single crystal X‐ray data collection. We thank Ms. Yanfei Niu and Prof. Xiaoli Zhao at East China Normal University for collecting the X‐ray data for compound . 3 Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = jul,

day = "27",

doi = "10.1002/anie.202004867",

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T1 - Excitonically Coupled Cyclic BF2 Arrays of Calix[8]- and Calix[16]phyrin as Near-IR-Chromophores

AU - Kim, Taeyeon

AU - Duan, Zhiming

AU - Talukdar, Sangita

AU - Lei, Chuanhu

AU - Kim, Dongho

AU - Sessler, Jonathan L.

AU - Sarma, Tridib

N1 - Funding Information: The work in Shanghai was supported by Shanghai University, the National Natural Science Foundation of China (no. 21901155 to C. L.), and the Eastern Scholars program from the Shanghai Municipal Education Committee (to C.L.). The work at Yonsei University was supported by the National Research Foundation of Korea (NRF) through a grant funded by the South Korean government (MEST) (No. 2016R1E1A1A01943379 to D.K.). The quantum mechanical calculations were supported by the National Institute of Supercomputing and Network (NISN)/Korea Institute of Science and Technology Information (KISTI) with needed supercomputing resources, including technical support (KSC‐2019‐CRE‐0201). The work in Austin was supported by the U.S. National Science Foundation (CHE‐1807152 to J.L.S.) and the Robert A. Welch Foundation (F‐0018 to J.L.S.). We thank the staff of Beamline BL17B1 at the National Facility for Protein Science Shanghai and the Shanghai Synchrotron Radiation Facility for assistance during the single crystal X‐ray data collection. We thank Ms. Yanfei Niu and Prof. Xiaoli Zhao at East China Normal University for collecting the X‐ray data for compound . 3 Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/7/27

Y1 - 2020/7/27

N2 - 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.

AB - 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.

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