Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

Kang Cai; Yi Shi; Changsu Cao; Suneal Vemuri; Binbin Cui; Dengke Shen; Huang Wu; Long Zhang; Yunyan Qiu; Hongliang Chen; Yang Jiao; Charlotte L. Stern; Fehaid M. Alsubaie; Hai Xiao; Jun Li; J. Fraser Stoddart

doi:10.1039/c9sc04860j

Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

Kang Cai, Yi Shi, Changsu Cao, Suneal Vemuri, Binbin Cui, Dengke Shen, Huang Wu, Long Zhang, Yunyan Qiu, Hongliang Chen, Yang Jiao, Charlotte L. Stern, Fehaid M. Alsubaie, Hai Xiao, Jun Li, J. Fraser Stoddart^*

^*Corresponding author for this work

Chemistry

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

16 Scopus citations

Abstract

Although host-guest pairing interactions between bisradical dicationic cyclobis(paraquat-p-phenylene) (BB²⁽⁺⁾) and the bipyridinium radical cation (BIPY⁺) have been studied extensively, host molecules other than BB²⁽⁺⁾ are few and far between. Herein, four bisradical dicationic cyclophanes with tunable cavity sizes are investigated as new bisradical dicationic hosts for accommodating the methyl viologen radical cation (MV⁺) to form trisradical tricationic complexes. The structure-property relationships between cavity sizes and binding affinities have been established by comprehensive solution and solid-state characterizations as well as DFT calculations. The association constants of the four new trisradical tricationic complexes are found to range between 7400 and 170 000 M^-1, with the strongest one being 4.3 times higher than that for [MV⊂BB]³⁽⁺⁾. The facile accessibility and tunable stability of these new trisradical tricationic complexes make them attractive redox-controlled recognition motifs for further use in supramolecular chemistry and mechanostereochemistry.

Original language	English (US)
Pages (from-to)	107-112
Number of pages	6
Journal	Chemical Science
Volume	11
Issue number	1
DOIs	https://doi.org/10.1039/c9sc04860j
State	Published - 2020

Funding

This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University. This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University.

ASJC Scopus subject areas

General Chemistry

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10.1039/c9sc04860j

Cite this

@article{752b300f518c492188203bc8cf026dc9,

title = "Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes",

abstract = "Although host-guest pairing interactions between bisradical dicationic cyclobis(paraquat-p-phenylene) (BB2(+)) and the bipyridinium radical cation (BIPY+) have been studied extensively, host molecules other than BB2(+) are few and far between. Herein, four bisradical dicationic cyclophanes with tunable cavity sizes are investigated as new bisradical dicationic hosts for accommodating the methyl viologen radical cation (MV+) to form trisradical tricationic complexes. The structure-property relationships between cavity sizes and binding affinities have been established by comprehensive solution and solid-state characterizations as well as DFT calculations. The association constants of the four new trisradical tricationic complexes are found to range between 7400 and 170 000 M-1, with the strongest one being 4.3 times higher than that for [MV⊂BB]3(+). The facile accessibility and tunable stability of these new trisradical tricationic complexes make them attractive redox-controlled recognition motifs for further use in supramolecular chemistry and mechanostereochemistry.",

author = "Kang Cai and Yi Shi and Changsu Cao and Suneal Vemuri and Binbin Cui and Dengke Shen and Huang Wu and Long Zhang and Yunyan Qiu and Hongliang Chen and Yang Jiao and Stern, {Charlotte L.} and Alsubaie, {Fehaid M.} and Hai Xiao and Jun Li and {Fraser Stoddart}, J.",

note = "Funding Information: This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University. Funding Information: This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University. Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

year = "2020",

doi = "10.1039/c9sc04860j",

language = "English (US)",

volume = "11",

pages = "107--112",

journal = "Chemical Science",

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publisher = "Royal Society of Chemistry",

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T1 - Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

AU - Cai, Kang

AU - Shi, Yi

AU - Cao, Changsu

AU - Vemuri, Suneal

AU - Cui, Binbin

AU - Shen, Dengke

AU - Wu, Huang

AU - Zhang, Long

AU - Qiu, Yunyan

AU - Chen, Hongliang

AU - Jiao, Yang

AU - Stern, Charlotte L.

AU - Alsubaie, Fehaid M.

AU - Xiao, Hai

AU - Li, Jun

AU - Fraser Stoddart, J.

N1 - Funding Information: This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by the So and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University. Funding Information: This research is part of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work utilized Northwestern University Micro/Nano Fabrication Facility (NUFAB), which is partially supported by the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the Materials Research Science and Engineering Center (DMR-1720139), the State of Illinois, and Northwestern University. Publisher Copyright: © 2019 The Royal Society of Chemistry.

PY - 2020

Y1 - 2020

N2 - Although host-guest pairing interactions between bisradical dicationic cyclobis(paraquat-p-phenylene) (BB2(+)) and the bipyridinium radical cation (BIPY+) have been studied extensively, host molecules other than BB2(+) are few and far between. Herein, four bisradical dicationic cyclophanes with tunable cavity sizes are investigated as new bisradical dicationic hosts for accommodating the methyl viologen radical cation (MV+) to form trisradical tricationic complexes. The structure-property relationships between cavity sizes and binding affinities have been established by comprehensive solution and solid-state characterizations as well as DFT calculations. The association constants of the four new trisradical tricationic complexes are found to range between 7400 and 170 000 M-1, with the strongest one being 4.3 times higher than that for [MV⊂BB]3(+). The facile accessibility and tunable stability of these new trisradical tricationic complexes make them attractive redox-controlled recognition motifs for further use in supramolecular chemistry and mechanostereochemistry.

AB - Although host-guest pairing interactions between bisradical dicationic cyclobis(paraquat-p-phenylene) (BB2(+)) and the bipyridinium radical cation (BIPY+) have been studied extensively, host molecules other than BB2(+) are few and far between. Herein, four bisradical dicationic cyclophanes with tunable cavity sizes are investigated as new bisradical dicationic hosts for accommodating the methyl viologen radical cation (MV+) to form trisradical tricationic complexes. The structure-property relationships between cavity sizes and binding affinities have been established by comprehensive solution and solid-state characterizations as well as DFT calculations. The association constants of the four new trisradical tricationic complexes are found to range between 7400 and 170 000 M-1, with the strongest one being 4.3 times higher than that for [MV⊂BB]3(+). The facile accessibility and tunable stability of these new trisradical tricationic complexes make them attractive redox-controlled recognition motifs for further use in supramolecular chemistry and mechanostereochemistry.

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U2 - 10.1039/c9sc04860j

DO - 10.1039/c9sc04860j

M3 - Article

C2 - 32110362

AN - SCOPUS:85076977163

SN - 2041-6520

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EP - 112

JO - Chemical Science

JF - Chemical Science

IS - 1

ER -

Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

Abstract

Funding

ASJC Scopus subject areas

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CCDC 1955704: Experimental Crystal Structure Determination

CCDC 1955711: Experimental Crystal Structure Determination

CCDC 1955706: Experimental Crystal Structure Determination

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Tuning radical interactions in trisradical tricationic complexes by varying host-cavity sizes

Abstract

Funding

ASJC Scopus subject areas

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Datasets

CCDC 1955704: Experimental Crystal Structure Determination

CCDC 1955711: Experimental Crystal Structure Determination

CCDC 1955706: Experimental Crystal Structure Determination

Cite this