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Issue 25, 2011
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Electronic structure and absorption spectra of supramolecular complexes of a fullerene crown ether with a π-extended TTF derivative

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Abstract

The present work is a theoretical investigation on supramolecular complexes of a fullerene crown ether (A and B isomers) with a derivative of π-extended tetrathiafulvalene (T). The geometry and the electronic structure of seven different conformers of the complex of dibenzo-18-crown-6 ether of fullero-N-methylpyrrolidine with a N-benzyl-N-(4-{[9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracen-2-yl]ethynyl}benzyl)ammonium cation were determined. We calculated the complexation energies and the absorption spectra, i.e., the lowest 50 excited electronic states of the complexes have been determined at the ground state optimum geometry. All calculations were carried out employing the density functional theory (DFT) and the time-dependent DFT, using the B3LYP, CAM-B3LYP, ωB97X-D, and M06-2X functionals in conjunction with the 6-31G(d,p) basis set. Various types of van der Waals interactions are observed in the complexes. Conformer complexation energies (CE) range from 2.54 to 2.14 eV in the gas phase and from 1.75 to 1.34 eV in CHCl3 solvent at the ωB97X-D/6-31G(d,p)//M06-2X/6-31G(d,p) level of theory. There are three major features at about 390, 330, and 290 nm in the calculated absorption spectra of all the conformers. The major peaks correspond to TT, TT/F (electron density in both T and the fullerene F of B) and to TF transitions, depending on the particular conformer. Other charge transfer TF transitions are observed close to the TT transition, indicating the possibility of photoinduced electron transfer in all these complexes.

Graphical abstract: Electronic structure and absorption spectra of supramolecular complexes of a fullerene crown ether with a π-extended TTF derivative

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Publication details

The article was received on 25 Nov 2010, accepted on 05 May 2011 and first published on 31 May 2011


Article type: Paper
DOI: 10.1039/C0CP02665D
Citation: Phys. Chem. Chem. Phys., 2011,13, 11965-11975

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    Electronic structure and absorption spectra of supramolecular complexes of a fullerene crown ether with a π-extended TTF derivative

    D. Tzeli, I. D. Petsalakis and G. Theodorakopoulos, Phys. Chem. Chem. Phys., 2011, 13, 11965
    DOI: 10.1039/C0CP02665D

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