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Complexation and Electronic Communication between Corannulene‐Based Buckybowls and a Curved Truxene‐TTF Donor
Author(s) -
Gallego María,
Calbo Joaquín,
Krick Calderon Rafael M.,
Pla Paula,
Hsieh YaChu,
Pérez Emilio M.,
Wu YaoTing,
Ortí Enrique,
Guldi Dirk M.,
Martín Nazario
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201604921
Subject(s) - corannulene , chemistry , materials science , molecule , organic chemistry
The association behavior of an electron‐donating, bowl‐shaped, truxene‐based tetrathiafulvalene (truxTTF) with two corannulene‐based fullerene fragments, C 32 H 12 and C 38 H 14 , 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 log K a =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. Time‐dependent 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 C 32 H 12 or C 38 H 14 and their supramolecular associates with truxTTF. In the case of truxTTF⋅C 38 H 14 , photoexcitation yields the charge‐separated state truxTTF .+ ⋅C 38 H 14 .− with a lifetime of approximately 160 ps.