Popov Alexey A, Burtsev Alexander V, Senyavin Vladimir M, Dunsch Lothar, Troyanov Sergey I
Chemistry Department, Moscow State University, Moscow 119992, Russia.
J Phys Chem A. 2009 Jan 8;113(1):263-72. doi: 10.1021/jp805264q.
The first spectroscopic characterization of the dimeric dicationic fullerene complex (C(70))(2)(Ti(3)Cl(13))(-)(2) is reported and supported by DFT calculations. The IR spectrum of the dimer is interpreted in terms of the normal modes of the pristine C(70), and the effects of charging C(70) and the intercage bond formation between C(70) units on the IR spectrum are discussed. Analysis of the vibrational spectrum of the anion, Ti(3)Cl(13)(-), is also provided. NIR absorption and fluorescence spectra of the complex are studied, and the dimer is shown to have a small HOMO-LUMO gap of 0.8 eV. The electronic structure of (C(70))(2) is studied with the use of DFT and compared to that of the other single-bonded fullerene dimers, including (C(70))(2), (C(69)N)(2), and (C(60))(2). Characteristic features in the vibrational spectra and electronic structure of all single-bonded fullerene dimers are revealed.
报道了二聚双阳离子富勒烯配合物(C(70))(2)(Ti(3)Cl(13))(-)(2)的首次光谱表征，并得到了密度泛函理论（DFT）计算的支持。根据原始C(70)的正常模式对二聚体的红外光谱进行了解释，并讨论了C(70)带电以及C(70)单元之间笼间键形成对红外光谱的影响。还提供了阴离子Ti(3)Cl(13)(-)的振动光谱分析。研究了该配合物的近红外吸收光谱和荧光光谱，结果表明该二聚体的最高占据分子轨道（HOMO）与最低未占据分子轨道（LUMO）之间的能隙较小，为0.8电子伏特。利用DFT研究了(C(70))(2)的电子结构，并与其他单键富勒烯二聚体的电子结构进行了比较，包括(C(70))(2)、(C(69)N)(2)和(C(60))(2)。揭示了所有单键富勒烯二聚体振动光谱和电子结构的特征。
