Behavior of fullerene C70 in binary organic solvent mixtures as studied using UV-Vis spectra and dynamic light scattering

N. A. Marfunin, N. Mchedlov-Petrossyan
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引用次数: 1

Abstract

In this paper, the formation of colloidal species of fullerene C70 in organic solvents was studied. The examining of the UV-visible spectra was accompanied by particle size analysis using dynamic light scattering, DLS. Stock solutions of C70 in non-polar toluene and n-hexane were diluted with polar solvents acetonitrile and methanol. The appearance of colloidal species with a size within the range of ≈50–500 nm is accompanied by alterations of the absorption spectra. In the toluene–acetonitrile and toluene–methanol binary mixed solvents at 25 oC, the absorption spectra of C70 (5×10–6 M) tend to retain the features of the spectrum in neat aromatic solvent even if the C70 molecules are gathered into colloidal aggregates. Earlier such phenomenon was observed for C60 in benzene–acetonitrile and toluene–methanol solvent systems. This gives support to the idea of rather stable primary solvate shells formed by aromatic molecules around the fullerene molecules. The behavior of C70 in toluene mixtures with methanol was compared with the earlier reported results from this laboratory for the C60 fullerene in the same solvent system. The study of n-hexane–methanol mixtures was performed at elevated temperature because of limited miscibility of these solvents at 25 oC. Accordingly, the C70–toluene–methanol system was also examined at 40 oC. A small but distinctly noticeable difference was revealed. Whereas in the case of the last-named system, the absorption spectrum typical for molecular form of C70 is still observable when colloidal species are already present in the solution, the turning-point between molecules and colloids as determined by both UV-visible spectra and DLS coincides for the n-hexane–methanol binary mixed solvent. Hence, the solvation shells formed by the aliphatic solvent around C70 are less stable as compared with those formed by toluene. Finally, the absorption spectra of C70 in the mixed solvents toluene–n-hexane were analyzed. These data give some support to the assumption of preferable solvation of the C70 molecules by the aromatic co-solvent.
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用紫外可见光谱和动态光散射研究了富勒烯C70在二元有机溶剂混合物中的行为
本文研究了富勒烯C70在有机溶剂中的胶体形成。紫外-可见光谱的检查伴随着使用动态光散射DLS的粒度分析。C70在非极性甲苯和正己烷中的储备溶液用极性溶剂乙腈和甲醇稀释。尺寸在≈50–500 nm范围内的胶体物质的出现伴随着吸收光谱的变化。在25℃的甲苯-乙腈和甲苯-甲醇二元混合溶剂中,即使C70分子聚集成胶体聚集体,C70(5×10–6 M)的吸收光谱也倾向于保留纯芳香溶剂中的光谱特征。早期在苯-乙腈和甲苯-甲醇溶剂体系中观察到C60存在这种现象。这支持了由富勒烯分子周围的芳香分子形成的相当稳定的初级溶剂化物壳层的想法。C70在甲苯和甲醇混合物中的行为与该实验室在相同溶剂系统中C60富勒烯的早期报告结果进行了比较。正己烷-甲醇混合物的研究是在高温下进行的,因为这些溶剂在25℃下的混溶性有限。因此,C70–甲苯–甲醇系统也在40℃下进行了检查。发现了一个微小但明显的差异。然而,在最后命名的系统的情况下,当溶液中已经存在胶体物质时,分子形式C70的典型吸收光谱仍然可以观察到,通过紫外-可见光谱和DLS确定的分子和胶体之间的转折点与正己烷-甲醇二元混合溶剂相一致。因此,与甲苯形成的溶剂化壳相比,由C70周围的脂族溶剂形成的溶剂合壳不太稳定。最后,分析了C70在甲苯-正己烷混合溶剂中的吸收光谱。这些数据为C70分子通过芳族共溶剂优选溶剂化的假设提供了一些支持。
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