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

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)-[Co ^III (nEGEspy) ₂ (3,6-DTBSQ)(3,6-DTBCat)] (ls-[Co ^III ], 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-[Co ^III ] transitioned into a green liquid, accompanied by an almost complete VT shift (94 %) to the high-spin (hs)-[Co ^II (nEGEspy) ₂ (3,6-DTBSQ) ₂ ] (hs-[Co ^II ]) upon melting. In contrast, violet crystals of Co4EGEspy and Co6EGEspy in the ls-[Co ^III ] 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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