DFT study of the interaction free energy of p–p complexes of fullerenes with buckybowls and viologen dimers

Girolamo Casella, Giacomo Saielli, Girolamo Casella

Risultato della ricerca: Article

29 Citazioni (Scopus)

Abstract

We present a theoretical investigation, by means of DFT protocols, of the complexation thermodynamics of (i) complexes of C70 and C60 fullerenes with bowl-shaped hexabenzocoronene derivatives and (ii) complexes of C60 with viologen dimers. The recent functionals of the M06 family, accounting for p–p interactions to a good level of approximation, have been used to calculate the interaction free energies. For the former complexes, the good agreement between the calculated results and the experimental data confirms the reliability of the protocol used. On these grounds, we then checked the stability of a series of complexes of C60 with some viologen dimers, 1BPnBP1 (n = 6–9), where two N-methylated bipyridinium units are linked by an alkyl chain of variable length, acting as molecular tweezers. Both forms of the viologen cores, that is the cation (each core doubly charged) and the reduced neutral form, were considered. For a suitable chain length a free energy gain upon complexation is predicted for the neutral form while the complexation of C60 by the cationic form is disfavoured mainly for entropic reasons.
Lingua originaleEnglish
pagine (da-a)1453-1459
Numero di pagine7
RivistaNew Journal of Chemistry
Volume35
Stato di pubblicazionePublished - 2011

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Viologens
Discrete Fourier transforms
Dimers
Free energy
Fullerenes
Complexation
Chain length
Positive ions
Cations

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Materials Chemistry
  • Chemistry(all)

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DFT study of the interaction free energy of p–p complexes of fullerenes with buckybowls and viologen dimers. / Casella, Girolamo; Saielli, Giacomo; Casella, Girolamo.

In: New Journal of Chemistry, Vol. 35, 2011, pag. 1453-1459.

Risultato della ricerca: Article

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title = "DFT study of the interaction free energy of p–p complexes of fullerenes with buckybowls and viologen dimers",
abstract = "We present a theoretical investigation, by means of DFT protocols, of the complexation thermodynamics of (i) complexes of C70 and C60 fullerenes with bowl-shaped hexabenzocoronene derivatives and (ii) complexes of C60 with viologen dimers. The recent functionals of the M06 family, accounting for p–p interactions to a good level of approximation, have been used to calculate the interaction free energies. For the former complexes, the good agreement between the calculated results and the experimental data confirms the reliability of the protocol used. On these grounds, we then checked the stability of a series of complexes of C60 with some viologen dimers, 1BPnBP1 (n = 6–9), where two N-methylated bipyridinium units are linked by an alkyl chain of variable length, acting as molecular tweezers. Both forms of the viologen cores, that is the cation (each core doubly charged) and the reduced neutral form, were considered. For a suitable chain length a free energy gain upon complexation is predicted for the neutral form while the complexation of C60 by the cationic form is disfavoured mainly for entropic reasons.",
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T1 - DFT study of the interaction free energy of p–p complexes of fullerenes with buckybowls and viologen dimers

AU - Casella, Girolamo

AU - Saielli, Giacomo

AU - Casella, Girolamo

PY - 2011

Y1 - 2011

N2 - We present a theoretical investigation, by means of DFT protocols, of the complexation thermodynamics of (i) complexes of C70 and C60 fullerenes with bowl-shaped hexabenzocoronene derivatives and (ii) complexes of C60 with viologen dimers. The recent functionals of the M06 family, accounting for p–p interactions to a good level of approximation, have been used to calculate the interaction free energies. For the former complexes, the good agreement between the calculated results and the experimental data confirms the reliability of the protocol used. On these grounds, we then checked the stability of a series of complexes of C60 with some viologen dimers, 1BPnBP1 (n = 6–9), where two N-methylated bipyridinium units are linked by an alkyl chain of variable length, acting as molecular tweezers. Both forms of the viologen cores, that is the cation (each core doubly charged) and the reduced neutral form, were considered. For a suitable chain length a free energy gain upon complexation is predicted for the neutral form while the complexation of C60 by the cationic form is disfavoured mainly for entropic reasons.

AB - We present a theoretical investigation, by means of DFT protocols, of the complexation thermodynamics of (i) complexes of C70 and C60 fullerenes with bowl-shaped hexabenzocoronene derivatives and (ii) complexes of C60 with viologen dimers. The recent functionals of the M06 family, accounting for p–p interactions to a good level of approximation, have been used to calculate the interaction free energies. For the former complexes, the good agreement between the calculated results and the experimental data confirms the reliability of the protocol used. On these grounds, we then checked the stability of a series of complexes of C60 with some viologen dimers, 1BPnBP1 (n = 6–9), where two N-methylated bipyridinium units are linked by an alkyl chain of variable length, acting as molecular tweezers. Both forms of the viologen cores, that is the cation (each core doubly charged) and the reduced neutral form, were considered. For a suitable chain length a free energy gain upon complexation is predicted for the neutral form while the complexation of C60 by the cationic form is disfavoured mainly for entropic reasons.

KW - DFT; buckybowls; fullerene; viologen dimers

UR - http://hdl.handle.net/10447/54755

M3 - Article

VL - 35

SP - 1453

EP - 1459

JO - New Journal of Chemistry

JF - New Journal of Chemistry

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