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X-ray diffraction and Raman study of pressure-assisted photopolymerization in the ferrocene-doped C60 crystals

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Abstract

The pressure-assisted photopolymerization in the fullerene complex with ferrocene C60·{Fe(C5H5)2}2 was studied for the first time by simultaneous in-situ Raman and X-ray diffraction (XRD) techniques at pressures up to 8 GPa. The irreversible splitting of the Ag(2) mode in the Raman spectra, resembling pristine fullerene polymerization, was observed at 4.6 GPa. The structural analysis does not show the formation of covalent bonds between adjacent fullerene molecules at a pressure up to 5 GPa. The unit cell volume and interfullerene distances are smooth and monotonous functions of pressure, and the shortest interfullerene distance 9.4 Å at 5 GPa significantly exceeds 9.06 Å typical of fullerene polymers. The changes in the Raman spectra at 4.6 GPa grow with the laser power and exposure time, showing typical photopolymerization phenomena. The distance between ferrocene and fullerene molecules decreases linearly with pressure changing the slope at 2 GPa due to intermolecular interaction crossover. The length of a ferrocene molecule in the complex increases with pressure in contrast to its decrease in a pristine ferrocene crystal. This behavior is associated with a change in the charge state of an iron atom and indicates a charge transfer from ferrocene to fullerene molecules.

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Acknowledgments

This work is carried out within the state task of ISSP.

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Authors and Affiliations

  1. Institute of Solid State Physics RAS, Chernogolovka, Moscow region, 142432, Russia

    K. P. Meletov, A. V. Kuzmin & S. S. Khasanov

  2. Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow region, 142432, Russia

    D. V. Konarev

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  1. K. P. Meletov
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  2. A. V. Kuzmin
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  3. S. S. Khasanov
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  4. D. V. Konarev
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Correspondence to K. P. Meletov.

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Meletov, K.P., Kuzmin, A.V., Khasanov, S.S. et al. X-ray diffraction and Raman study of pressure-assisted photopolymerization in the ferrocene-doped C60 crystals. J Polym Res 28, 38 (2021). https://doi.org/10.1007/s10965-021-02411-6

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  • DOI: https://doi.org/10.1007/s10965-021-02411-6

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