Tunable Synchronicity of Molecular Valence Tautomerism with Macroscopic Solid-Liquid Transition by Molecular Lattice Engineering |
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Authors: | Mayumi Chida Satoru Takahashi Ryunosuke Konishi Dr. Takeshi Matsumoto Dr. Akinobu Nakada Dr. Masanori Wakizaka Dr. Wataru Kosaka Prof. Hitoshi Miyasaka Prof. Ho-Chol Chang |
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Affiliation: | 1. Department of Applied Chemistry Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga Bunkyo-ku, Tokyo, 112-8551 Japan;2. Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577 Japan |
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Abstract: | 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 ConEGEspy (n = 2, 4, and 6). These complexes commonly form violet crystals of the low-spin (ls)-[CoIII(nEGEspy)2(3,6-DTBSQ)(3,6-DTBCat)] (ls-[CoIII], 3,6-DTBSQ = 3,6-di-tert-butyl semiquinonato, 3,6-DTBCat = 3,6-di-tert-butyl catecholato). Interestingly, violet crystals of Co2EGEspy in the ls-[CoIII] transitioned into a green liquid, accompanied by an almost complete VT shift (94 %) to the high-spin (hs)-[CoII(nEGEspy)2(3,6-DTBSQ)2] (hs-[CoII]) upon melting. In contrast, violet crystals of Co4EGEspy and Co6EGEspy in the ls-[CoIII] 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. |
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Keywords: | cobalt crystal engineering N,O ligands phase transitions valence isomerization |
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