Self-assembly of supramolecular fullerene ribbons via hydrogen-bonding interactions and their impact on fullerene electronic interactions and charge carrier mobility.
The anisotropy of the electronic interactions between fullerenes in crystalline solids was examined using a confocal fluorescence microscope by probing the polarization of the fluorescence emission arising from fullerene excimer-like emitting states. Crystals of C(60) obtained by vacuum-sublimation or from chloroform solution exhibited no or little polarization (p = 0 or 0.11, respectively), as expected from the high symmetry of the C(60) fcc lattice or the low degree of anisotropy induced by included solvent molecules. The use of hydrogen-bonding to supramolecularly control interfullerene electronic interactions was explored using a fullerene derivative (1) combining a solubilizing 3,4-di-tert-butylbenzene group and a barbituric acid hydrogen-bonding (H-B) moiety. The crystal structure of 1 establishes the existence of fullerene H-B tapes along which interfullerene electronic interactions are expected to be large. In agreement with this, we observe very strong polarization of the fullerene excimer-like emission (p = 0.78), indicative of a high degree of anisotropy in the fullerene interactions. The charge-carrier mobility of 1 as determined from OFET devices was found to be lower than that of C(60) (1.2 x 10(-4) vs 1.2 x 10(-2) cm(2)/s V), which is rationalized on the basis of the reduced dimensionality of 1 as a wire-like semiconductor and variations in the morphology of the device active layer revealed by AFM measurements.
Chu
Cheng-Che
CC
Institut des Sciences Moléculaires, CNRS UMR 5255, Université Bordeaux 1, 33405 Talence, France.
Raffy
Guillaume
G
Ray
Debdas
D
Del Guerzo
André
A
Kauffmann
Brice
B
Wantz
Guillaume
G
Hirsch
Lionel
L
Bassani
Dario M
DM
D016880:Anisotropy; D001463:Barbiturates / Q000737:chemistry*; D004583:Electrons; D037741:Fullerenes / Q000737:chemistry*; D006860:Hydrogen Bonding; D046911:Macromolecular Substances / Q000138:chemical synthesis / Q000737:chemistry; D018613:Microscopy, Confocal
D001463:Barbiturates; D037741:Fullerenes; D046911:Macromolecular Substances; C069837:fullerene C60; C032232:barbituric acid