Complexation and electronic communication between corannulene-based buckybowls and a curved truxene-TTF donor

María Gallego, Joaquín Calbo, Rafael M.Krick Calderon, Paula Pla, Ya Chu Hsieh, Emilio M. Pérez, Yao-Ting Wu, Enrique Ortí, Dirk M. Guldi, Nazario Martín

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12 and C38H14, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range logKa=2.9–3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of π–π and CH–π interactions is the driving force for association. Timedependent DFT calculations reproduce the experimental UV/ Vis titrations and provide a detailed understanding of the spectral changes observed. Femtosecond transient absorption studies reveal the processes occurring after photoexcitation of either C32H12 or C38H14 and their supramolecular associates with truxTTF. In the case of truxTTF·C38H14, photoexcitation yields the charge-separated state truxTTFC+·C38H14·-with a lifetime of approximately 160 ps.

Original languageEnglish
Pages (from-to)3666-3673
Number of pages8
JournalChemistry - A European Journal
Volume23
Issue number15
DOIs
Publication statusPublished - 2017 Jan 1

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Complexation
Density functional theory
Photoexcitation
Titration
Communication
Association reactions
Fullerenes
Conformations
Nuclear magnetic resonance
Derivatives
Electrons
corannulene
tetrathiafulvalene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

Gallego, M., Calbo, J., Calderon, R. M. K., Pla, P., Hsieh, Y. C., Pérez, E. M., ... Martín, N. (2017). Complexation and electronic communication between corannulene-based buckybowls and a curved truxene-TTF donor. Chemistry - A European Journal, 23(15), 3666-3673. https://doi.org/10.1002/chem.201604921
Gallego, María ; Calbo, Joaquín ; Calderon, Rafael M.Krick ; Pla, Paula ; Hsieh, Ya Chu ; Pérez, Emilio M. ; Wu, Yao-Ting ; Ortí, Enrique ; Guldi, Dirk M. ; Martín, Nazario. / Complexation and electronic communication between corannulene-based buckybowls and a curved truxene-TTF donor. In: Chemistry - A European Journal. 2017 ; Vol. 23, No. 15. pp. 3666-3673.
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abstract = "The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12 and C38H14, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range logKa=2.9–3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of π–π and CH–π interactions is the driving force for association. Timedependent DFT calculations reproduce the experimental UV/ Vis titrations and provide a detailed understanding of the spectral changes observed. Femtosecond transient absorption studies reveal the processes occurring after photoexcitation of either C32H12 or C38H14 and their supramolecular associates with truxTTF. In the case of truxTTF·C38H14, photoexcitation yields the charge-separated state truxTTFC+·C38H14·-with a lifetime of approximately 160 ps.",
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Gallego, M, Calbo, J, Calderon, RMK, Pla, P, Hsieh, YC, Pérez, EM, Wu, Y-T, Ortí, E, Guldi, DM & Martín, N 2017, 'Complexation and electronic communication between corannulene-based buckybowls and a curved truxene-TTF donor', Chemistry - A European Journal, vol. 23, no. 15, pp. 3666-3673. https://doi.org/10.1002/chem.201604921

Complexation and electronic communication between corannulene-based buckybowls and a curved truxene-TTF donor. / Gallego, María; Calbo, Joaquín; Calderon, Rafael M.Krick; Pla, Paula; Hsieh, Ya Chu; Pérez, Emilio M.; Wu, Yao-Ting; Ortí, Enrique; Guldi, Dirk M.; Martín, Nazario.

In: Chemistry - A European Journal, Vol. 23, No. 15, 01.01.2017, p. 3666-3673.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Complexation and electronic communication between corannulene-based buckybowls and a curved truxene-TTF donor

AU - Gallego, María

AU - Calbo, Joaquín

AU - Calderon, Rafael M.Krick

AU - Pla, Paula

AU - Hsieh, Ya Chu

AU - Pérez, Emilio M.

AU - Wu, Yao-Ting

AU - Ortí, Enrique

AU - Guldi, Dirk M.

AU - Martín, Nazario

PY - 2017/1/1

Y1 - 2017/1/1

N2 - The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12 and C38H14, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range logKa=2.9–3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of π–π and CH–π interactions is the driving force for association. Timedependent DFT calculations reproduce the experimental UV/ Vis titrations and provide a detailed understanding of the spectral changes observed. Femtosecond transient absorption studies reveal the processes occurring after photoexcitation of either C32H12 or C38H14 and their supramolecular associates with truxTTF. In the case of truxTTF·C38H14, photoexcitation yields the charge-separated state truxTTFC+·C38H14·-with a lifetime of approximately 160 ps.

AB - The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12 and C38H14, is investigated in several solvents. Formation of 1:1 complexes is followed by absorption titrations and complemented by density functional theory (DFT) calculations. The binding constants are in the range logKa=2.9–3.5. DFT calculations reveal that the most stable arrangement is the conformation in which the 1,3-dithiole ring of truxTTF is placed inside the concave cavity of the corannulene derivative. This arrangement is confirmed experimentally by NMR measurements, and implies that a combination of π–π and CH–π interactions is the driving force for association. Timedependent DFT calculations reproduce the experimental UV/ Vis titrations and provide a detailed understanding of the spectral changes observed. Femtosecond transient absorption studies reveal the processes occurring after photoexcitation of either C32H12 or C38H14 and their supramolecular associates with truxTTF. In the case of truxTTF·C38H14, photoexcitation yields the charge-separated state truxTTFC+·C38H14·-with a lifetime of approximately 160 ps.

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