摘要
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.
| 原文 | English |
|---|---|
| 頁（從 - 到） | 3666-3673 |
| 頁數 | 8 |
| 期刊 | Chemistry - A European Journal |
| 卷 | 23 |
| 發行號 | 15 |
| DOIs | |
| 出版狀態 | Published - 2017 一月 1 |
指紋
All Science Journal Classification (ASJC) codes
- Catalysis
- Organic Chemistry
引用此文
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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.
於: Chemistry - A European Journal, 卷 23, 編號 15, 01.01.2017, p. 3666-3673.研究成果: Article
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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U2 - 10.1002/chem.201604921
DO - 10.1002/chem.201604921
M3 - Article
C2 - 28075509
AN - SCOPUS:85013271913
VL - 23
SP - 3666
EP - 3673
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 15
ER -