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Fullertubes are tubular fullerenes with nanotube-like middle section and fullerene-like endcaps. To understand how this intermediate form between spherical fullerenes and nanotubes is reflected in the vibrational modes, we performed comprehensive studies of IR and Raman spectra of fullertubes C90-D5h, C96-D3d, and C100-D5d. An excellent agreement between experimental and DFT-computed spectra enabled a detailed vibrational assignment and allowed an analysis of the localization degree of the vibrational modes in different parts of fullertubes. Projection analysis was performed to establish an exact numerical correspondence between vibrations of the belt midsection and fullerene headcaps to the modes of nanotubes and fullerene C60-Ih. As a result, we could not only identify fullerene-like and CNT-like vibrations of fullertubes, but also trace their origin in specific vibrational modes of CNT and C60-Ih. IR spectra were found to be dominated by vibrations of fullerene-like caps resembling IR-active modes of C60-Ih, whereas in Raman spectra both caps and belt vibrations are found to be equally active. Unlike the resonance Raman spectra of CNTs, in which only two single-phonon bands are detected, the Raman spectra of fullertubes exhibit several CNT-like vibrations and thus provide additional information on nanotube phonons. 

Tremendous progress in the development of single molecule magnets (SMMs) raises the question of their device integration. On this route, understanding the properties of low‐dimensional assemblies of SMMs, in particular in contact with electrodes, is a necessary but difficult step. Here, it is shown that fullerene SMM self‐assembled on metal substrate from solution retains magnetic hysteresis up to 10 K. Fullerene‐SMM DySc₂N@C₈₀and Dy₂ScN@C₈₀are derivatized to introduce a thioacetate group, which is used to graft SMMs on gold. Magnetic properties of grafted SMMs are studied by X‐ray magnetic circular dichroism and compared to the films of nonderivatized fullerenes prepared by sublimation. In self‐assembled films, the magnetic moments of the Dy ions are preferentially aligned parallel to the surface, which is different from the disordered orientation of endohedral clusters in nonfunctionalized fullerenes. Whereas chemical derivatization reduces the blocking temperature of magnetization and narrows the hysteresis of Dy₂ScN@C₈₀, for DySc₂N@C₈₀equally broad hysteresis is observed as in the fullerene multilayer. Magnetic bistability in the DySc₂N@C₈₀grafted on gold is sustained up to 10 K. This study demonstrates that self‐assembly of fullerene‐SMM derivatives offers a facile solution‐based procedure for the preparation of functional magnetic sub‐monolayers with excellent SMM performance.

 

Herein, we report the first example of a crystalline metal–donor–fullerene framework, in which control of the donor–fullerene mutual orientation was achieved through chemical bond formation, in particular, by metal coordination. The¹³C cross‐polarization magic‐angle spinning NMR spectroscopy, X‐ray diffraction, and time‐resolved fluorescence spectroscopy were performed for comprehensive structural analysis and energy‐transfer (ET) studies of the fulleretic donor–acceptor scaffold. Furthermore, in combination with photoluminescence measurements, the theoretical calculations of the spectral overlap function, Förster radius, excitation energies, and band structure were employed to elucidate the photophysical and ET processes in the prepared fulleretic material. We envision that the well‐defined fulleretic donor–acceptor materials could contribute not only to the basic science of fullerene chemistry but would also be used towards effective development of organic photovoltaics and molecular electronics.