Radical Cyclic [3]Daisy Chains

Kang Cai; Binbin Cui; Bo Song; Heng Wang; Yunyan Qiu; Leighton O. Jones; Wenqi Liu; Yi Shi; Suneal Vemuri; Dengke Shen; Tianyu Jiao; Long Zhang; Huang Wu; Hongliang Chen; Yang Jiao; Yu Wang; Charlotte L. Stern; Hao Li; George C. Schatz; Xiaopeng Li; J. Fraser Stoddart

doi:10.1016/j.chempr.2020.11.004

Radical Cyclic [3]Daisy Chains

Kang Cai, Binbin Cui, Bo Song, Heng Wang, Yunyan Qiu, Leighton O. Jones, Wenqi Liu, Yi Shi, Suneal Vemuri, Dengke Shen, Tianyu Jiao, Long Zhang, Huang Wu, Hongliang Chen, Yang Jiao, Yu Wang, Charlotte L. Stern, Hao Li, George C. Schatz, Xiaopeng LiJ. Fraser Stoddart^*

^*Corresponding author for this work

Chemistry

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

25 Scopus citations

Abstract

Mechanically interlocked molecules (MIMs) that undergo controllable internal motions of their component parts in more than one dimension are rare entities in the molecular world. Cyclic [2]daisy chains ([c2]DCs) are a class of MIMs that have been identified as prototypes for molecular muscles. It remains, however, a challenge to synthesize [cn]DCs with n > 2 selectively and efficiently. Herein, we report the design and synthesis of [c3]DCs employing radical and anionic templates. Two mechanically interlocked [c3]DCs with 18 positive charges were obtained in >90% yields. One [c3]DC displayed good air stability in its radical cationic form, while the other underwent reversible “co-conformational” switching between open macrocyclic and closed trisarm-shaped forms under electrochemical control. These findings provide not only two-dimensional MIMs with attractive electronic and switchable properties, but also a starting point for the design of extended molecular arrays, which could become the forerunners of adjustable molecular nets and breathable molecular membranes.

Original language	English (US)
Pages (from-to)	174-189
Number of pages	16
Journal	Chem
Volume	7
Issue number	1
DOIs	https://doi.org/10.1016/j.chempr.2020.11.004
State	Published - Jan 14 2021

Funding

The authors thank Northwestern University (NU) for their support of this research. G.C.S., J.F.S., and L.O.J. were funded by the Center for Sustainable Separations of Metals (CSSM), a National Science Foundation (NSF) Center for Chemical Innovation (CCI), grant number CHE-1925708 . The research made use of the IMSERC X-ray facility at NU, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource ( NSF ECCS-1542205) and NU. H.W. and X.L. acknowledge support from Shenzhen University and the University of South Florida . H.L. acknowledges support from the National Natural Science Foundation of China (nos. 21772173 , 91856116 , and 21922108 ), the Natural Science Foundation of Zhejiang Province (no. LR18B020001 ), and the “ Fundamental Research Funds for the Central Universities ” (no. 2019FZA3007 ). The authors thank Northwestern University (NU) for their support of this research. G.C.S. J.F.S. and L.O.J. were funded by the Center for Sustainable Separations of Metals (CSSM), a National Science Foundation (NSF) Center for Chemical Innovation (CCI), grant number CHE-1925708. The research made use of the IMSERC X-ray facility at NU, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205) and NU. H.W. and X.L. acknowledge support from Shenzhen University and the University of South Florida. H.L. acknowledges support from the National Natural Science Foundation of China (nos. 21772173, 91856116, and 21922108), the Natural Science Foundation of Zhejiang Province (no. LR18B020001), and the ?Fundamental Research Funds for the Central Universities? (no. 2019FZA3007). K.C. and J.F.S. conceived the idea and designed the experiments. K.C. B.C. Y.S. S.V. T.J. and H.L. synthesized the materials. K.C. characterized the materials with the help of D.S. H. Wu, H.C. Y.J. and Y.W.; B.S. H. Wang, and X.L. performed the MS analyses. L.O.J. and G.C.S. did the DFT calculations. W.L. performed the IGM analysis. Y.Q. and L.Z. carried out the CPE experiments. C.L.S. performed the X-ray diffraction measurements. K.C. and J.F.S. wrote the first and subsequent drafts of the manuscript. J.F.S. supervised the project. All authors discussed the results and commented on the manuscript. The authors declare no competing interests.

Keywords

SDG9: Industry, innovation, and infrastructure
anion templation
cyclic macromolecules
mechanically interlocked molecules
molecular daisy chains
radical chemistry
redox-controlled switching
supramolecular daisy chains

ASJC Scopus subject areas

General Chemistry
Biochemistry
Environmental Chemistry
General Chemical Engineering
Biochemistry, medical
Materials Chemistry

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10.1016/j.chempr.2020.11.004

Cite this

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title = "Radical Cyclic [3]Daisy Chains",

abstract = "Mechanically interlocked molecules (MIMs) that undergo controllable internal motions of their component parts in more than one dimension are rare entities in the molecular world. Cyclic [2]daisy chains ([c2]DCs) are a class of MIMs that have been identified as prototypes for molecular muscles. It remains, however, a challenge to synthesize [cn]DCs with n > 2 selectively and efficiently. Herein, we report the design and synthesis of [c3]DCs employing radical and anionic templates. Two mechanically interlocked [c3]DCs with 18 positive charges were obtained in >90% yields. One [c3]DC displayed good air stability in its radical cationic form, while the other underwent reversible “co-conformational” switching between open macrocyclic and closed trisarm-shaped forms under electrochemical control. These findings provide not only two-dimensional MIMs with attractive electronic and switchable properties, but also a starting point for the design of extended molecular arrays, which could become the forerunners of adjustable molecular nets and breathable molecular membranes.",

keywords = "SDG9: Industry, innovation, and infrastructure, anion templation, cyclic macromolecules, mechanically interlocked molecules, molecular daisy chains, radical chemistry, redox-controlled switching, supramolecular daisy chains",

author = "Kang Cai and Binbin Cui and Bo Song and Heng Wang and Yunyan Qiu and Jones, {Leighton O.} and Wenqi Liu and Yi Shi and Suneal Vemuri and Dengke Shen and Tianyu Jiao and Long Zhang and Huang Wu and Hongliang Chen and Yang Jiao and Yu Wang and Stern, {Charlotte L.} and Hao Li and Schatz, {George C.} and Xiaopeng Li and Stoddart, {J. Fraser}",

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AU - Cai, Kang

AU - Cui, Binbin

AU - Song, Bo

AU - Wang, Heng

AU - Qiu, Yunyan

AU - Jones, Leighton O.

AU - Liu, Wenqi

AU - Shi, Yi

AU - Vemuri, Suneal

AU - Shen, Dengke

AU - Jiao, Tianyu

AU - Zhang, Long

AU - Wu, Huang

AU - Chen, Hongliang

AU - Jiao, Yang

AU - Wang, Yu

AU - Stern, Charlotte L.

AU - Li, Hao

AU - Schatz, George C.

AU - Li, Xiaopeng

AU - Stoddart, J. Fraser

PY - 2021/1/14

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N2 - Mechanically interlocked molecules (MIMs) that undergo controllable internal motions of their component parts in more than one dimension are rare entities in the molecular world. Cyclic [2]daisy chains ([c2]DCs) are a class of MIMs that have been identified as prototypes for molecular muscles. It remains, however, a challenge to synthesize [cn]DCs with n > 2 selectively and efficiently. Herein, we report the design and synthesis of [c3]DCs employing radical and anionic templates. Two mechanically interlocked [c3]DCs with 18 positive charges were obtained in >90% yields. One [c3]DC displayed good air stability in its radical cationic form, while the other underwent reversible “co-conformational” switching between open macrocyclic and closed trisarm-shaped forms under electrochemical control. These findings provide not only two-dimensional MIMs with attractive electronic and switchable properties, but also a starting point for the design of extended molecular arrays, which could become the forerunners of adjustable molecular nets and breathable molecular membranes.

AB - Mechanically interlocked molecules (MIMs) that undergo controllable internal motions of their component parts in more than one dimension are rare entities in the molecular world. Cyclic [2]daisy chains ([c2]DCs) are a class of MIMs that have been identified as prototypes for molecular muscles. It remains, however, a challenge to synthesize [cn]DCs with n > 2 selectively and efficiently. Herein, we report the design and synthesis of [c3]DCs employing radical and anionic templates. Two mechanically interlocked [c3]DCs with 18 positive charges were obtained in >90% yields. One [c3]DC displayed good air stability in its radical cationic form, while the other underwent reversible “co-conformational” switching between open macrocyclic and closed trisarm-shaped forms under electrochemical control. These findings provide not only two-dimensional MIMs with attractive electronic and switchable properties, but also a starting point for the design of extended molecular arrays, which could become the forerunners of adjustable molecular nets and breathable molecular membranes.

KW - SDG9: Industry, innovation, and infrastructure

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Radical Cyclic [3]Daisy Chains

Abstract

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Keywords

ASJC Scopus subject areas

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CCDC 1986261: Experimental Crystal Structure Determination

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Radical Cyclic [3]Daisy Chains

Abstract

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1986261: Experimental Crystal Structure Determination

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