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Tunable Synchronicity of Molecular Valence Tautomerism with Macroscopic Solid‐Liquid Transition by Molecular Lattice Engineering
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- Mayumi Chida
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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- Satoru Takahashi
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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- Ryunosuke Konishi
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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- Takeshi Matsumoto
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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- Akinobu Nakada
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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- Masanori Wakizaka
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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- Wataru Kosaka
- Institute for Materials Research Tohoku University 2-1-1 Katahira, Aoba-ku Sendai 980-8577 Japan
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- Hitoshi Miyasaka
- Institute for Materials Research Tohoku University 2-1-1 Katahira, Aoba-ku Sendai 980-8577 Japan
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- Ho‐Chol Chang
- Department of Applied Chemistry Faculty of Science and Engineering Chuo University 1-13-27 Kasuga Bunkyo-ku Tokyo 112-8551 Japan
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Description
<jats:title>Abstract</jats:title><jats:p>The combination of a cobalt‐dioxolene core that exhibits valence tautomerism (VT) with pyridine‐3,5‐dicarboxylic acid functionalized with chains bearing two, four, or six oxyethylene units led to new complexes <jats:bold>Co<jats:italic>n</jats:italic>EGEspy</jats:bold> (<jats:italic>n</jats:italic> = 2, 4, and 6). These complexes commonly form violet crystals of the <jats:italic>low‐spin</jats:italic> (<jats:italic>ls</jats:italic>)‐[Co<jats:sup>III</jats:sup>(<jats:italic>n</jats:italic>EGEspy)<jats:sub>2</jats:sub>(3,6‐DTBSQ)(3,6‐DTBCat)] (<jats:italic>ls‐</jats:italic>[Co<jats:sup>III</jats:sup>], 3,6‐DTBSQ = 3,6‐di‐<jats:italic>tert</jats:italic>‐butyl semiquinonato, 3,6‐DTBCat = 3,6‐di‐<jats:italic>tert</jats:italic>‐butyl catecholato). Interestingly, violet crystals of <jats:bold>Co2EGEspy</jats:bold> in the <jats:italic>ls‐</jats:italic>[Co<jats:sup>III</jats:sup>] transitioned into a green liquid, accompanied by an almost complete VT shift (94 %) to the <jats:italic>high‐spin</jats:italic> (<jats:italic>hs</jats:italic>)‐[Co<jats:sup>II</jats:sup>(<jats:italic>n</jats:italic>EGEspy)<jats:sub>2</jats:sub>(3,6‐DTBSQ)<jats:sub>2</jats:sub>] (<jats:italic>hs‐</jats:italic>[Co<jats:sup>II</jats:sup>]) upon melting. In contrast, violet crystals of <jats:bold>Co4EGEspy</jats:bold> and <jats:bold>Co6EGEspy</jats:bold> in the <jats:italic>ls‐</jats:italic>[Co<jats:sup>III</jats:sup>] exhibited partial VT (33 %) and only a 9.3 % VT shift after melting, respectively. These data demonstrate the tunability of the synchronicity of the molecular VT and macroscopic solid‐liquid transitions by optimizing the tethered chains, thus establishing a new strategy for coupling bistable molecules with the macroscopic world.</jats:p>
Journal
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- Chemistry – A European Journal
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Chemistry – A European Journal 27 (66), 16354-16366, 2021-10-19
Wiley