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- Lebedkin, S., et al.
(författare)
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Dimerization of C70 under high pressure : thermal dissociation and photophysical properties of the dimer C140
- 2000
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Ingår i: Electronic properties od novel materials-molecular nanostructures. - Meville, NY : American Institute of Physics (AIP). - 1563969734 ; , s. 77-80
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Konferensbidrag (refereegranskat)abstract
- We have recently shown that solid C70 efficiently converts into a cap-to-cap dimer C2hC140 at pressure of ~1 GPa and temperature of ~200 °C [1]. Here we report on measurements of the thermal dissociation of C140 (purified by chromatography) at ambient pressure and its photophysical properties, in particular photogeneration of singlet oxygen (1O2). The kinetics of dissociation of C140 in the solid state between 130 and 200 °C is well described by a simple first-order process, with an activation energy of 1.6±0.03 eV (compare to 1.75±0.05 eV for the C60 dimer C120 [2]). In contrast, the thermal dissociation of C140 dissolved in o-dichlorobenzene shows different, non-Arrhenius behavior, suggesting a strong influence of the molecular surroundings. The quantum efficiency of 1O2 generation in solutions of C140 and C120 is close to unity, i.e. similar to that of C70 and C60.
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2. |
- Lebedkin, S., et al.
(författare)
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Structure and properties of the fullerene dimer C140 produced by pressure treatment of C70
- 2000
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 104:17, s. 4101-4110
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Tidskriftsartikel (refereegranskat)abstract
- A [2+2] cycloaddition cap-to-cap C70 dimer with C2h molecular symmetry was synthesized in high yield by pressure treatment of polycrystalline C70 at 1 GPa and 200° C. It was separated from unreacted monomers by chromatography and characterized by 13C NMR, Raman, and infrared spectroscopy, and other methods. Remarkably, only one isomer was produced out of the five possible [2+2] cycloaddition products which have equally low formation energies according to semiempirical modeling calculations. The dimer obtained is the one favored when C70 molecules adopt an ordered packing with parallel D5 axes. The intercage bonding in C140, its thermal stability, and intercage vibrational modes are similar to those found for the C60 dimer, C120. Both dimers photodissociate to the monomers in solution, probably via excited triplet states. The UV absorption and fluorescence properties of C140 are not very different from those of C70, suggesting only weak electronic interactions between the two cages of C140. In comparison, the pressure-induced dimerization of C60, under the conditions used for C70, results mainly in C60 oligomers and polymeric chains, but the dimer C120 could be isolated at low yield when short reaction times (≤5 min) were used.
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