Reactivity of fullerenes family towards radicals in terms of local curvature

Sabirov, Denis Sh.; Булгаков, Р. Г.

doi:10.1016/j.comptc.2010.10.016

Cited by 43 publications

(26 citation statements)

References 18 publications

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“…Spin density in adduct 1 is strongly delocalized on many of the fullerene carbon atoms, but about 40% of the spin density is distributed on only three atoms and has maximum values on atoms 2, 4, and 11 (values of spin density higher than 0.02 a.u. are shown in Table for structure 1 ), that is, the results for positions of 1,2 and 1,4, relative to the attached (macro)radical, are consistent with the results of other theoretical and experimental studies . Full results may be found in Supporting Information.…”

Section: Methodssupporting

confidence: 87%

“…This program and method allows us to obtain accurate energy and structural characteristics for the fullerene and its derivatives. These methods have been illustrated in several previous studies . Comparison of the geometrical characteristics of the C 60 molecule and the ionization energy calculated by various quantum chemical methods is given in Table .…”

Section: Methodsmentioning

confidence: 99%

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Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C₆₀ fullerene

Diniakhmetova

Friesen

Колесов

2016

Int J of Quantum Chemistry

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Modeling of the addition of various radicals to C 60 fullerene is currently an active research area. However, the radicals considered are not able to adequately model polymeric radicals. In this work, we have performed a theoretical study of the possible reactions of C 60 fullerene with 1-n-phenylpropyl radicals, which are used to model polystyrene radicals. Several possible ways of subsequent addition of up to four 1-phenylpropyl radicals to C 60 have been analyzed, the structures of the intermediates have been defined and thermal properties, such as the activation enthalpies of the corresponding reactions, have been calculated using density functional theory with the approximation of PBE/3z. It is shown that the topology of the spin density distribution on the fullerenyl radical causes regioselectivity for further radical addition. According to the energetic characteristics of the reactions, we assume the possibility of formation of products of one-, two-, three-, and four-addition of the growth radical to the fullerene core in radical polymerization of styrene in the presence of C 60 fullerene.

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Section: Methodssupporting

confidence: 87%

Section: Methodsmentioning

confidence: 99%

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C₆₀ fullerene

Diniakhmetova

Friesen

Колесов

2016

Int J of Quantum Chemistry

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“…The calculations were performed with the PBE/3z [12] method implemented in the Priroda 09 program [13]. According to previous works [14][15][16][17], this method accurately describes both the energy and structural parameters of the C 60 fullerene and its derivatives.…”

Section: Theoretical Methodologymentioning

confidence: 99%

Reactivity of short radicals at the initial stages of radical polymerization of allyl chloride: Chain growth versus addition to fullerene

Diniakhmetova

Yumagulova

Колесов

2021

Int J of Quantum Chemistry

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A quantum-chemical study of the C 60 interaction with various radicals generated from monomers in radical polymerization is significant in the fundamental aspects.However, the interactions between fullerene and radicals formed from allyl monomers has been poorly studied. Using the modern density functional theory methods, we performed quantum-chemical simulation on the C 60 interaction with the radicals arising upon the initial stages of the allyl chloride polymerization. We have found that the addition of growth radicals (with 1-4 monomer units) to C 60 are more favorable than the chain growth reactions. Herewith, the radicals with 2-4 monomer units are most reactive in the addition reaction. Our quantum-chemical findings explain the features of the initial stages of the allyl chloride radical polymerization in the presence of C 60 , namely, the increasing inhibition degree of the radical copolymerization of allyl chloride with methyl methacrylate and increasing induction period of copolymerization with styrene.

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“…A similar study was reported more recently for C 70 . 23 Sabirov et al 24,25 performed theoretical calculations using the PBE functional with a split-valence triple-zeta basis set for the addition of ozone to a range of fullerenes from C 20 to C 76 . The authors noted a direct correlation between the reaction energy and the radius of fullerene curvature at the site of ozone addition, with POZ formation on high-curvature fullerenes leading to larger exothermicity.…”

Section: Introductionmentioning

confidence: 99%

A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions

Chapleski

Morris

Troya

2014

Phys. Chem. Chem. Phys.

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We present an investigation of the reaction of ozone with C60 fullerene using electronic structure methods. Motivated by recent experiments of ozone exposure to a C60 film, we have characterized stationary points in the potential energy surface for the reactions of O3 with C60 that include both the formation of primary ozonide and subsequent dissociation reactions of this intermediate that lead to C-C bond cleavage. We have also investigated the addition of multiple O3 molecules to the C60 cage to explore potential reaction pathways under the high ozone flux conditions used in recent experiments. The lowest-energy product of the reaction of a single ozone molecule with C60 that results in C-C bond breakage corresponds to an open-cage C60O3 structure that contains ester and ketone moieties at the seam. This open-cage product is of much lower energy than the C60O + O2 products identified in prior work, and it is consistent with IR experimental spectra. Subsequent reaction of the open-cage C60O3 product with a second ozone molecule opens a low-energy reaction pathway that results in cage degradation via the loss of a CO2 molecule. Our calculations also reveal that, while full ozonation of all bonds between hexagons in C60 is unlikely even under high ozone concentration, the addition of a few ozone molecules to the C60 cage is favorable at room temperature.

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Reactivity of fullerenes family towards radicals in terms of local curvature

Cited by 43 publications

References 18 publications

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C₆₀ fullerene

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C₆₀ fullerene

Reactivity of short radicals at the initial stages of radical polymerization of allyl chloride: Chain growth versus addition to fullerene

A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions

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Reactivity of fullerenes family towards radicals in terms of local curvature

Cited by 43 publications

References 18 publications

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C60 fullerene

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C60 fullerene

Reactivity of short radicals at the initial stages of radical polymerization of allyl chloride: Chain growth versus addition to fullerene

A theoretical study of the ozonolysis of C60: primary ozonide formation, dissociation, and multiple ozone additions

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Product

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Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C₆₀ fullerene

Quantum chemical modeling of the addition reactions of 1‐n‐phenylpropyl radicals to C₆₀ fullerene

A theoretical study of the ozonolysis of C₆₀: primary ozonide formation, dissociation, and multiple ozone additions