Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins.
Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins.
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DOI：
10.1021/acs.langmuir.0c02427
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发表时间：
2020-11
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影响因子：
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通讯作者：
Mitsuhiko Morisue;G. Saito;Daiki Sasada;T. Umeyama;H. Imahori;K. Mitamura;H. Masunaga;T. Hoshino;S. Sakurai;S. Sasaki
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作者：
Mitsuhiko Morisue;G. Saito;Daiki Sasada;T. Umeyama;H. Imahori;K. Mitamura;H. Masunaga;T. Hoshino;S. Sakurai;S. Sasaki
探索了以液化卟啉（1和2）为基质对C60富勒烯的形貌控制。缓慢蒸发卟啉和C60在甲苯中的等摩尔混合物的溶剂，得到摩尔比为3：1的卟啉/C60复合物。化学计量结合行为表明，特定的卟啉-C60相互作用操作的卟啉/C60复合材料的形成，证实了光谱和热性能，和玻璃入射广角X-射线衍射。在体相条件下，分子识别的多重结合协同效应的传统热力学优势不太可能解释化学计量结合行为。相反，我们提出了一个大小匹配的影响，卟啉-C60相互作用的散装卟啉矩阵，即，“超分子溶剂化”。卟啉基质的玻璃态性质通过特定的相互作用传递到C60，卟啉/C60复合物在室温下呈玻璃态。
Morphological control of C60 fullerene using liquefied porphyrins (1 and 2) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C60 in toluene afforded the porphyrin/C60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C60 interactions operate the formation of the porphyrin/C60 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-C60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C60 through the specific interaction, and the porphyrin/C60 composites adopted glassy states at room temperature.