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- Title
Thermally Induced Intra-Carboxyl Proton Shuttle in a Molecular Rack-and-Pinion Cascade Achieving Macroscopic Crystal Deformation.
- Authors
Huang, You‐Gui; Shiota, Yoshihito; Su, Sheng‐Qun; Wu, Shu‐Qi; Yao, Zi‐Shuo; Li, Guo‐Ling; Kanegawa, Shinji; Kang, Soonchul; Kamachi, Takashi; Yoshizawa, Kazunari; Ariga, Katsuhiko; Sato, Osamu
- Abstract
Proton transport via dynamic molecules is ubiquitous in chemistry and biology. However, its use as a switching mechanism for properties in functional molecular assemblies is far less common. In this study, we demonstrate how an intra-carboxyl proton shuttle can be generated in a molecular assembly akin to a rack-and-pinion cascade via a thermally induced single-crystal-to-single-crystal phase transition. In a triply interpenetrated supramolecular organic framework (SOF), a 4,4′-azopyridine (azpy) molecule connects to two biphenyl-3,3′,5,5′-tetracarboxylic acid (H4BPTC) molecules to form a functional molecular system with switchable mechanical properties. A temperature change reversibly triggers a molecular movement akin to a rack-and-pinion cascade, which mainly involves 1) an intra-carboxyl proton shuttle coupled with tilting of the azo molecules and azo pedal motion and 2) H4BPTC translation. Moreover, both the molecular motions are collective, and being propagated across the entire framework, leading to a macroscopic crystal expansion and contraction.
- Subjects
PROTON therapy; PROTONS; SINGLE crystals; SUPRAMOLECULAR organometallic chemistry; COMPOSITE particles (Nuclear particles)
- Publication
Angewandte Chemie International Edition, 2016, Vol 55, Issue 47, p14628
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201607886