Radically Enhanced Dual Recognition

Xiao Yang Chen, Haochuan Mao, Yuanning Feng, Kang Cai, Dengke Shen, Huang Wu, Long Zhang, Xingang Zhao, Hongliang Chen, Bo Song, Yang Jiao, Yong Wu, Charlotte L. Stern, Michael R. Wasielewski, J. Fraser Stoddart*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Complexation between a viologen radical cation (V.+) and cyclobis(paraquat-p-phenylene) diradical dication (CBPQT2(.+)) has been investigated and utilized extensively in the construction of mechanically interlocked molecules (MIMs) and artificial molecular machines (AMMs). The selective recognition of a pair of V.+ using radical-pairing interactions, however, remains a formidable challenge. Herein, we report the efficient encapsulation of two methyl viologen radical cations (MV.+) in a size-matched bisradical dicationic host — namely, cyclobis(paraquat-2,6-naphthalene)2(.+), i.e., CBPQN2(.+). Central to this dual recognition process was the choice of 2,6-bismethylenenaphthalene linkers for incorporation into the bisradical dicationic host. They provide the space between the two bipyridinium radical cations in CBPQN2(.+) suitable for binding two MV.+ with relatively short (3.05–3.25 Å) radical-pairing distances. The size-matched bisradical dicationic host was found to exhibit highly selective and cooperative association with the two MV.+ in MeCN at room temperature. The formation of the tetrakisradical tetracationic inclusion complex — namely, [(MV)2⊂CBPQN]4(.+) – in MeCN was confirmed by VT 1H NMR, as well as by EPR spectroscopy. The solid-state superstructure of [(MV)2⊂CBPQN]4(.+) reveals an uneven distribution of the binding distances (3.05, 3.24, 3.05 Å) between the three different V.+, suggesting that localization of the radical-pairing interactions has a strong influence on the packing of the two MV.+ inside the bisradical dicationic host. Our findings constitute a rare example of binding two radical guests with high affinity and cooperativity using host-guest radical-pairing interactions. Moreover, they open up possibilities of harnessing the tetrakisradical tetracationic inclusion complex as a new, orthogonal and redox-switchable recognition motif for the construction of MIMs and AMMs.

Original languageEnglish (US)
Pages (from-to)25454-25462
Number of pages9
JournalAngewandte Chemie - International Edition
Volume60
Issue number48
DOIs
StatePublished - Nov 22 2021

Keywords

  • binding stoichiometry
  • host-guest systems
  • molecular recognition
  • radical-pairing interactions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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