Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States

Ruiquan Li; Chun-Hong Mak; Ke Luo; Fei Wang; Guopeng Liu; Bingbin Tan; Gen Liu; Yajie Xu; Yu-Dong Yang; Huiqi Wei; Zhengxi Huang; Lamei Wu; Xinyun Zhao; Hsien-Yi Hsu; Qing He; Jonathan L. Sessler; Zhan Zhang

doi:10.1021/jacs.3c10695

Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States

Ruiquan Li
, Chun-Hong Mak
, Ke Luo
, Fei Wang
, Guopeng Liu
, Bingbin Tan
, Gen Liu
, Yajie Xu
, Yu-Dong Yang
, Huiqi Wei
, Zhengxi Huang
, Lamei Wu
, Xinyun Zhao
, Hsien-Yi Hsu^*
, Qing He^*
, Jonathan L. Sessler^*
, Zhan Zhang^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

3 Citations (Scopus)

Abstract

We report here an expanded porphyrinoid, cyclo[2]pyridine[8]pyrrole, 1, that can exist at three closed-shell oxidation levels. Macrocycle 1 was synthesized via the oxidative coupling of two open chain precursors and fully characterized by means of NMR and UV-vis spectroscopies, MS, and X-ray crystallography. Reduction of the fully oxidized form (1, blue) with NaBH₄ produced either the half-oxidized (2, teal) or fully reduced forms (3, pale yellow), depending on the amount of reducing agent used and the presence or absence of air. Reduced products 2 or 3 can be oxidized to 1 by various oxidants (quinones, FeCl₃, and AgPF₆). Macrocycle 1 also undergoes proton-coupled reductions with I^-, Br^-, Cl^-, SO₃^2-, or S₂O₃^2- in the presence of an acid. Certain thiol-containing compounds likewise reduce 1 to 2 or 3. This conversion is accompanied by a readily discernible color change, making cyclo[2]pyridine[8]pyrrole 1 able to differentiate biothiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). © 2024 American Chemical Society.

Original language	English
Pages (from-to)	3585-3590
Journal	Journal of the American Chemical Society
Volume	146
Issue number	6
Online published	5 Feb 2024
DOIs	https://doi.org/10.1021/jacs.3c10695
Publication status	Published - 14 Feb 2024

Funding

The authors acknowledge financial support from the National Natural Science Foundation of China (22171289 to Z.Z.), Fundamental Research Funds for the Central Universities (Startup Funds to Q.H.), the Innovation and Technology Commission (Grant No. MHP/104/21 to H.Y.H.), the Shenzhen Science Technology and Innovation Commission (Grant No. JCYJ20210324125612035 to H.Y.H.), the City University of Hong Kong (Grant Nos. 9360140, 7005720, 9667229, 9680331, 7005580, and 9678291 to H.Y.H.), and the Robert A. Welch Foundation (Grant No. F-0018 to J.L.S.).

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Li, R., Mak, C.-H., Luo, K., Wang, F., Liu, G., Tan, B., Liu, G., Xu, Y., Yang, Y.-D., Wei, H., Huang, Z., Wu, L., Zhao, X., Hsu, H.-Y., He, Q., Sessler, J. L., & Zhang, Z. (2024). Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States. Journal of the American Chemical Society, 146(6), 3585-3590. https://doi.org/10.1021/jacs.3c10695

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title = "Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States",

abstract = "We report here an expanded porphyrinoid, cyclo[2]pyridine[8]pyrrole, 1, that can exist at three closed-shell oxidation levels. Macrocycle 1 was synthesized via the oxidative coupling of two open chain precursors and fully characterized by means of NMR and UV-vis spectroscopies, MS, and X-ray crystallography. Reduction of the fully oxidized form (1, blue) with NaBH4 produced either the half-oxidized (2, teal) or fully reduced forms (3, pale yellow), depending on the amount of reducing agent used and the presence or absence of air. Reduced products 2 or 3 can be oxidized to 1 by various oxidants (quinones, FeCl3, and AgPF6). Macrocycle 1 also undergoes proton-coupled reductions with I-, Br-, Cl-, SO32-, or S2O32- in the presence of an acid. Certain thiol-containing compounds likewise reduce 1 to 2 or 3. This conversion is accompanied by a readily discernible color change, making cyclo[2]pyridine[8]pyrrole 1 able to differentiate biothiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). {\textcopyright} 2024 American Chemical Society.",

author = "Ruiquan Li and Chun-Hong Mak and Ke Luo and Fei Wang and Guopeng Liu and Bingbin Tan and Gen Liu and Yajie Xu and Yu-Dong Yang and Huiqi Wei and Zhengxi Huang and Lamei Wu and Xinyun Zhao and Hsien-Yi Hsu and Qing He and Sessler, \{Jonathan L.\} and Zhan Zhang",

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T1 - Cyclo[2]pyridine[8]pyrrole

T2 - An Expanded Porphyrinoid with Three Closed-Shell Oxidation States

AU - Li, Ruiquan

AU - Mak, Chun-Hong

AU - Luo, Ke

AU - Wang, Fei

AU - Liu, Guopeng

AU - Tan, Bingbin

AU - Liu, Gen

AU - Xu, Yajie

AU - Yang, Yu-Dong

AU - Wei, Huiqi

AU - Huang, Zhengxi

AU - Wu, Lamei

AU - Zhao, Xinyun

AU - Hsu, Hsien-Yi

AU - He, Qing

AU - Sessler, Jonathan L.

AU - Zhang, Zhan

PY - 2024/2/14

Y1 - 2024/2/14

N2 - We report here an expanded porphyrinoid, cyclo[2]pyridine[8]pyrrole, 1, that can exist at three closed-shell oxidation levels. Macrocycle 1 was synthesized via the oxidative coupling of two open chain precursors and fully characterized by means of NMR and UV-vis spectroscopies, MS, and X-ray crystallography. Reduction of the fully oxidized form (1, blue) with NaBH4 produced either the half-oxidized (2, teal) or fully reduced forms (3, pale yellow), depending on the amount of reducing agent used and the presence or absence of air. Reduced products 2 or 3 can be oxidized to 1 by various oxidants (quinones, FeCl3, and AgPF6). Macrocycle 1 also undergoes proton-coupled reductions with I-, Br-, Cl-, SO32-, or S2O32- in the presence of an acid. Certain thiol-containing compounds likewise reduce 1 to 2 or 3. This conversion is accompanied by a readily discernible color change, making cyclo[2]pyridine[8]pyrrole 1 able to differentiate biothiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). © 2024 American Chemical Society.

AB - We report here an expanded porphyrinoid, cyclo[2]pyridine[8]pyrrole, 1, that can exist at three closed-shell oxidation levels. Macrocycle 1 was synthesized via the oxidative coupling of two open chain precursors and fully characterized by means of NMR and UV-vis spectroscopies, MS, and X-ray crystallography. Reduction of the fully oxidized form (1, blue) with NaBH4 produced either the half-oxidized (2, teal) or fully reduced forms (3, pale yellow), depending on the amount of reducing agent used and the presence or absence of air. Reduced products 2 or 3 can be oxidized to 1 by various oxidants (quinones, FeCl3, and AgPF6). Macrocycle 1 also undergoes proton-coupled reductions with I-, Br-, Cl-, SO32-, or S2O32- in the presence of an acid. Certain thiol-containing compounds likewise reduce 1 to 2 or 3. This conversion is accompanied by a readily discernible color change, making cyclo[2]pyridine[8]pyrrole 1 able to differentiate biothiols, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). © 2024 American Chemical Society.

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U2 - 10.1021/jacs.3c10695

DO - 10.1021/jacs.3c10695

M3 - RGC 21 - Publication in refereed journal

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 6

ER -

Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States

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ResCtrs: College of Engineering Research Centre for Functional Photonics (CFP)

ITF: Large-area, High-performing and Stable Perovskite Light-emitting Didoes

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Cyclo[2]pyridine[8]pyrrole: An Expanded Porphyrinoid with Three Closed-Shell Oxidation States

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ResCtrs: College of Engineering Research Centre for Functional Photonics (CFP)

ITF: Large-area, High-performing and Stable Perovskite Light-emitting Didoes

Cite this