解决羟基化C60化学中长达三十年的错误归属

摘要(中文译文)

水溶性功能化富勒烯通常被称为富勒醇、富勒醇或多羟基富勒烯，广泛应用于光子学、催化和生物医学领域，然而近三十年来，人们一直假定其分子结构仅由羟基组成。尽管计算与实验的振动光谱和光学光谱之间以及预期与观察到的化学反应性之间持续存在不一致，这一假设仍然被维持。在此，我们结合傅里叶变换红外（FTIR）和吸收（UV-Vis）光谱、X射线光电子能谱（XPS）、靶向化学衍生化以及计算量子化学来解决这一差异。我们表明，只有一种包含反离子配位的羰基和半缩酮基团以及羟基的多氧富勒烯结构，才能同时重现特征性FTIR特征和实验UV-Vis吸收谱。纯羟基化富勒烯模型无法捕捉主导性FTIR谱带和不对称紫外吸收。肟形成实验从化学上验证了羰基和半缩酮基团的存在。这一结构重新归属解决了富勒烯化学中长期存在的不一致，纠正了文献中普遍存在的误解，并建立了一个合理调控功能化纳米碳光学和化学性质的框架。

Abstract

Water-soluble functionalized fullerenes commonly referred to as fullerenols, fullerols or polyhydroxy fullerenes are widely used in photonics, catalysis, and biomedicine, yet their molecular structures have been assumed to consist solely of hydroxyl groups for nearly three decades. This assumption remains despite persistent mismatches between calculated and experimental vibrational and optical spectra as well as expected and observed chemical reactivity. Here we combine Fourier transform infrared (FTIR) and absorption (UV-Vis) spectroscopy, X-ray photoelectron spectroscopy (XPS), targeted chemical derivatization, and computational quantum chemistry to resolve this discrepancy. We show that only a polyoxy-fullerene architecture incorporating counterion-coordinated carbonyl and hemiketal groups alongside hydroxyls reproduces both the characteristic FTIR features and the experimental UV-Vis absorption profile. A purely hydroxylated fullerene model fails to capture the dominant FTIR band and asymmetric ultraviolet absorption. Oxime-formation experiments chemically validate the presence of carbonyl and hemiketal groups. This structural reassignment resolves long-standing inconsistencies in fullerene chemistry, corrects a pervasive misinterpretation in the literature, and establishes a framework for rationally tuning the optical and chemical properties of functionalized nanocarbons.

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