Thermally-induced atropisomerism promotes metal-organic cage construction

热诱导阻转异构现象促进金属有机笼状结构的构建

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Abstract

Molecular folding regulation with environmental stimuli is critical in living and artificial molecular machine systems. Herein, we described a macrocycle, cyclo[4] (1,3-(4,6-dimethyl)benzene)[4](1,3-(4,6-dimethyl)benzene)(4-pyridine). Under 298 K, it has three stable stiff atropisomers with names as 1 (C(s) symmetry), 2 (C(s) symmetry), and 3 (C(4v) symmetry). At 393 K, 1 can reversibly transform into 2, but at 473 K, it can irrevocably transform into 3. At 338 K, 3 and (PhCN)(2)PdCl(2) complex to produce the metal-organic cage 4. Only at 338 K does the combination of 1 or 2 and (PhCN)(2)PdCl(2) create a gel-like structure. Heating both gels to 473 K transforms them into 4. In addition to offering a thermally accelerated method for modifying self-assembled systems using macrocyclic building blocks, this study also has the potential to develop the nanoscale transformation material with a thermal response.

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