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Molecular magnetic switch for a metallofullerene.

ABSTRACT: The endohedral fullerenes lead to well-protected internal species by the fullerene cages, and even highly reactive radicals can be stabilized. However, the manipulation of the magnetic properties of these radicals from outside remains challenging. Here we report a system of a paramagnetic metallofullerene Sc3C2@C80 connected to a nitroxide radical, to achieve the remote control of the magnetic properties of the metallofullerene. The remote nitroxide group serves as a magnetic switch for the electronic spin resonance (ESR) signals of Sc3C2@C80 via spin-spin interactions. Briefly, the nitroxide radical group can 'switch off' the ESR signals of the Sc3C2@C80 moiety. Moreover, the strength of spin-spin interactions between Sc3C2@C80 and the nitroxide group can be manipulated by changing the distance between these two spin centres. In addition, the ESR signals of the Sc3C2@C80 moiety can be switched on at low temperatures through weakened spin-lattice interactions.

SUBMITTER: Wu B

PROVIDER: S-EPMC4366484 | biostudies-literature | 2015 Mar

REPOSITORIES: biostudies-literature

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Molecular magnetic switch for a metallofullerene.

Wu Bo B Wang Taishan T Feng Yongqiang Y Zhang Zhuxia Z Jiang Li L Wang Chunru C

Nature communications 20150303

The endohedral fullerenes lead to well-protected internal species by the fullerene cages, and even highly reactive radicals can be stabilized. However, the manipulation of the magnetic properties of these radicals from outside remains challenging. Here we report a system of a paramagnetic metallofullerene Sc3C2@C80 connected to a nitroxide radical, to achieve the remote control of the magnetic properties of the metallofullerene. The remote nitroxide group serves as a magnetic switch for the elec ...[more]

PMID: 25732144

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Project description:We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of Y x Sc3-x N@C80 (x = 0-3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1-T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin-lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.

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Molecular magnetic switch for a metallofullerene.

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Molecular magnetic switch for a metallofullerene.

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