title: Complexation and Electronic Communication between Corannulene-Based Buckybowls and a Curved Truxene-TTF Donor.
abstract: The association behavior of an electron-donating, bowl-shaped, truxene-based tetrathiafulvalene (truxTTF) with two corannulene-based fullerene fragments, C32H12and 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 log Ka=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 C32H12or C38H14and their supramolecular associates with truxTTF. In the case of truxTTF⋅C38H14, photoexcitation yields the charge-separated state truxTTF.+⋅C38H14.-with a lifetime of approximately 160 ps.
authors.affiliation: Departamento de Química Orgánica, Fac. C. C. Químicas, Universidad Complutense de Madrid, Av. Complutense s/n, 28040, Madrid, Spain.
authors.forename: María
authors.initials: M
authors.lastname: Gallego
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, 46980, Paterna, Spain.
authors.forename: Joaquín
authors.initials: J
authors.lastname: Calbo
authors.affiliation: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität, Erlangen-Nürnberg, 91058, Erlangen, Germany.
authors.forename: Rafael M
authors.initials: RM
authors.lastname: Krick Calderon
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, 46980, Paterna, Spain.
authors.forename: Paula
authors.initials: P
authors.lastname: Pla
authors.affiliation: Department of Chemistry, National Cheng Kung University, 70101, Tainan, Taiwan.
authors.forename: Ya-Chu
authors.initials: YC
authors.lastname: Hsieh
authors.affiliation: IMDEA Nanociencia, Faraday 9, Campus UAM, 28049, Madrid, Spain.
authors.forename: Emilio M
authors.identifier: http://orcid.org/0000-0002-8739-2777
authors.initials: EM
authors.lastname: Pérez
authors.affiliation: Department of Chemistry, National Cheng Kung University, 70101, Tainan, Taiwan.
authors.forename: Yao-Ting
authors.initials: YT
authors.lastname: Wu
authors.affiliation: Instituto de Ciencia Molecular, Universidad de Valencia, 46980, Paterna, Spain.
authors.forename: Enrique
authors.identifier: http://orcid.org/0000-0001-9544-8286
authors.initials: E
authors.lastname: Ortí
authors.affiliation: Department of Chemistry and Pharmacy and Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität, Erlangen-Nürnberg, 91058, Erlangen, Germany.
authors.forename: Dirk M
authors.initials: DM
authors.lastname: Guldi
authors.affiliation: Departamento de Química Orgánica, Fac. C. C. Químicas, Universidad Complutense de Madrid, Av. Complutense s/n, 28040, Madrid, Spain.|IMDEA Nanociencia, Faraday 9, Campus UAM, 28049, Madrid, Spain.
authors.forename: Nazario
authors.initials: N
authors.lastname: Martín
keywords: association constants; buckybowls; donor-acceptor systems; photoinduced charge transfer; supramolecular chemistry