Fully Conjugated [4]Chrysaorene. Redox-Coupled Anion Binding in a Tetraradicaloid Macrocycle

Hanna Gregolińska; Marcin Majewski; Piotr J. Chmielewski; Janusz Gregoliński; Alan Chien; Jiawang Zhou; Yi-Lin Wu; Youn Jue Bae; Michael R. Wasielewski; Paul M. Zimmerman; Marcin Stepień

doi:10.1021/jacs.8b09385

Fully Conjugated [4]Chrysaorene. Redox-Coupled Anion Binding in a Tetraradicaloid Macrocycle

Hanna Gregolińska, Marcin Majewski, Piotr J. Chmielewski, Janusz Gregoliński, Alan Chien, Jiawang Zhou, Yi-Lin Wu, Youn Jue Bae, Michael R. Wasielewski^*, Paul M. Zimmerman, Marcin Stepień

^*Corresponding author for this work

Chemistry

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

29 Scopus citations

Abstract

[4]Chrysaorene, a fully conjugated carbocyclic coronoid, is shown to be a low-bandgap π-conjugated system with a distinct open-shell character. The system shows good chemical stability and can be oxidized to well-defined radical cation and dication states. The cavity of [4]chrysaorene acts as an anion receptor toward halide ions with a particular selectivity toward iodides (K_a = 207 ± 6 M^-1). The interplay between anion binding and redox chemistry is demonstrated using a ¹H NMR analysis in solution. In particular, a well-resolved, paramagnetically shifted spectrum of the [4]chrysaorene radical cation is observed, providing evidence for the inner binding of the iodide. The radical cation-iodide adduct can be generated in thin solid films of [4] chrysaorene by simple exposure to diiodine vapor.

Original language	English (US)
Pages (from-to)	14474-14480
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	140
Issue number	43
DOIs	https://doi.org/10.1021/jacs.8b09385
State	Published - Oct 31 2018

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Fully Conjugated [4]Chrysaorene. Redox-Coupled Anion Binding in a Tetraradicaloid Macrocycle",

abstract = "[4]Chrysaorene, a fully conjugated carbocyclic coronoid, is shown to be a low-bandgap π-conjugated system with a distinct open-shell character. The system shows good chemical stability and can be oxidized to well-defined radical cation and dication states. The cavity of [4]chrysaorene acts as an anion receptor toward halide ions with a particular selectivity toward iodides (Ka = 207 ± 6 M-1). The interplay between anion binding and redox chemistry is demonstrated using a 1H NMR analysis in solution. In particular, a well-resolved, paramagnetically shifted spectrum of the [4]chrysaorene radical cation is observed, providing evidence for the inner binding of the iodide. The radical cation-iodide adduct can be generated in thin solid films of [4] chrysaorene by simple exposure to diiodine vapor.",

author = "Hanna Gregoli{\'n}ska and Marcin Majewski and Chmielewski, {Piotr J.} and Janusz Gregoli{\'n}ski and Alan Chien and Jiawang Zhou and Yi-Lin Wu and Bae, {Youn Jue} and Wasielewski, {Michael R.} and Zimmerman, {Paul M.} and Marcin Stepie{\'n}",

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doi = "10.1021/jacs.8b09385",

language = "English (US)",

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AU - Gregolińska, Hanna

AU - Majewski, Marcin

AU - Chmielewski, Piotr J.

AU - Gregoliński, Janusz

AU - Chien, Alan

AU - Zhou, Jiawang

AU - Wu, Yi-Lin

AU - Bae, Youn Jue

AU - Wasielewski, Michael R.

AU - Zimmerman, Paul M.

AU - Stepień, Marcin

PY - 2018/10/31

Y1 - 2018/10/31

N2 - [4]Chrysaorene, a fully conjugated carbocyclic coronoid, is shown to be a low-bandgap π-conjugated system with a distinct open-shell character. The system shows good chemical stability and can be oxidized to well-defined radical cation and dication states. The cavity of [4]chrysaorene acts as an anion receptor toward halide ions with a particular selectivity toward iodides (Ka = 207 ± 6 M-1). The interplay between anion binding and redox chemistry is demonstrated using a 1H NMR analysis in solution. In particular, a well-resolved, paramagnetically shifted spectrum of the [4]chrysaorene radical cation is observed, providing evidence for the inner binding of the iodide. The radical cation-iodide adduct can be generated in thin solid films of [4] chrysaorene by simple exposure to diiodine vapor.

AB - [4]Chrysaorene, a fully conjugated carbocyclic coronoid, is shown to be a low-bandgap π-conjugated system with a distinct open-shell character. The system shows good chemical stability and can be oxidized to well-defined radical cation and dication states. The cavity of [4]chrysaorene acts as an anion receptor toward halide ions with a particular selectivity toward iodides (Ka = 207 ± 6 M-1). The interplay between anion binding and redox chemistry is demonstrated using a 1H NMR analysis in solution. In particular, a well-resolved, paramagnetically shifted spectrum of the [4]chrysaorene radical cation is observed, providing evidence for the inner binding of the iodide. The radical cation-iodide adduct can be generated in thin solid films of [4] chrysaorene by simple exposure to diiodine vapor.

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Fully Conjugated [4]Chrysaorene. Redox-Coupled Anion Binding in a Tetraradicaloid Macrocycle

Abstract

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