Tunable Synchronicity of Molecular Valence Tautomerism with Macroscopic Solid-Liquid Transition by Molecular Lattice Engineering

Mayumi Chida, Satoru Takahashi, Ryunosuke Konishi, Takeshi Matsumoto, Akinobu Nakada, Masanori Wakizaka, Wataru Kosaka, Hitoshi Miyasaka, Ho Chol Chang

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)16354-16366
Number of pages13
JournalChemistry - A European Journal
Volume27
Issue number66
DOIs
Publication statusPublished - 2021 Nov 25

Keywords

  • N,O ligands
  • cobalt
  • crystal engineering
  • phase transitions
  • valence isomerization

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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