Stabilizing the Naphthalenediimide Radical within a Tetracationic Cyclophane

Tianyu Jiao, Kang Cai, Jordan N. Nelson, Yang Jiao, Yunyan Qiu, Guangcheng Wu, Jiawang Zhou, Chuyang Cheng, Dengke Shen, Yuanning Feng, Zhichang Liu, Michael R. Wasielewski, J. Fraser Stoddart, Hao Li

Research output: Contribution to journalArticle

Abstract

Organic radicals are of importance in developing smart materials that have paramagnetic and/or near-infrared optical properties. Their practical applications, however, are limited by the labile nature of the radicals. Here, we demonstrate that by using a tetracationic cyclophane, namely, cyclobis(4,4′-(1,4-phenylene)bispyridine-p-phenylene) (ExBox4+), to encapsulate a naphthalenediimide (NDI) guest, the redox properties of NDI can be modulated. In organic solvents such as MeCN or DMF, ExBox4+ is able to provide the surrounding Coulombic attraction to the NDI•- radical anion and therefore enhance its stability toward oxidation. In water, NDI•- is prone to dimerization, forming its (NDI•-)2 dimer. Under UV-light irradiation, the (NDI•-)2 dimer is observed to disproportionate and yield the dianionic NDI2-. ExBox4+ is able to encapsulate the NDI•- radical anion and prevent its dimerization, and as a consequence, the radical anion is protected from further reduction in a noncovalent manner. We believe that our strategy of modulating the redox properties of NDI by either host-guest recognition or mechanical interlocking can aid and abet the development of radical-based materials, which could be employed in pursuit of applications in many areas, such as transporting spin and charges.

Original languageEnglish
JournalJournal of the American Chemical Society
DOIs
Publication statusAccepted/In press - Jan 1 2019

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Negative ions
Dimerization
Dimers
Intelligent materials
Anions
Ultraviolet radiation
Organic solvents
Optical properties
Irradiation
Oxidation-Reduction
Infrared radiation
Oxidation
naphthalenediimide
Water
Ultraviolet Rays

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Stabilizing the Naphthalenediimide Radical within a Tetracationic Cyclophane. / Jiao, Tianyu; Cai, Kang; Nelson, Jordan N.; Jiao, Yang; Qiu, Yunyan; Wu, Guangcheng; Zhou, Jiawang; Cheng, Chuyang; Shen, Dengke; Feng, Yuanning; Liu, Zhichang; Wasielewski, Michael R.; Stoddart, J. Fraser; Li, Hao.

In: Journal of the American Chemical Society, 01.01.2019.

Research output: Contribution to journalArticle

Jiao, T, Cai, K, Nelson, JN, Jiao, Y, Qiu, Y, Wu, G, Zhou, J, Cheng, C, Shen, D, Feng, Y, Liu, Z, Wasielewski, MR, Stoddart, JF & Li, H 2019, 'Stabilizing the Naphthalenediimide Radical within a Tetracationic Cyclophane', Journal of the American Chemical Society. https://doi.org/10.1021/jacs.9b08926
Jiao, Tianyu ; Cai, Kang ; Nelson, Jordan N. ; Jiao, Yang ; Qiu, Yunyan ; Wu, Guangcheng ; Zhou, Jiawang ; Cheng, Chuyang ; Shen, Dengke ; Feng, Yuanning ; Liu, Zhichang ; Wasielewski, Michael R. ; Stoddart, J. Fraser ; Li, Hao. / Stabilizing the Naphthalenediimide Radical within a Tetracationic Cyclophane. In: Journal of the American Chemical Society. 2019.
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