Morisue Mitsuhiko, Saito Genki, Sasada Daiki, Umeyama Tomokazu, Imahori Hiroshi, Mitamura Koji, Masunaga Hiroyasu, Hoshino Taiki, Sakurai Shinichi, Sasaki Sono
Faculty of Molecular Chemistry and Engineering, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan.
Department of Molecular Engineering, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
Langmuir. 2020 Nov 17;36(45):13583-13590. doi: 10.1021/acs.langmuir.0c02427. Epub 2020 Nov 4.
Morphological control of C fullerene using liquefied porphyrins ( and ) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C in toluene afforded the porphyrin/C composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C interactions operate the formation of the porphyrin/C composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C through the specific interaction, and the porphyrin/C composites adopted glassy states at room temperature.
研究了以液化卟啉（和）为主体基质对C富勒烯的形态控制。卟啉与C在甲苯中的等摩尔混合物的溶剂缓慢蒸发，得到摩尔比为3:1的卟啉/C复合材料。化学计量结合行为表明，特定的卟啉-C相互作用控制了卟啉/C复合材料的形成，光谱和热性能以及掠入射广角X射线衍射证实了这一点。在本体条件下，分子识别中多重结合协同作用的传统热力学优势不太可能解释化学计量结合行为。相反，我们提出了本体卟啉基质中卟啉-C相互作用的尺寸匹配效应，即“超分子溶剂化”。卟啉基质的玻璃态通过特定相互作用传递给C，卟啉/C复合材料在室温下呈现玻璃态。
