TY - JOUR
T1 - Solid-state supramolecular organisation, established directly from powder diffraction data, and photoluminescence efficiency of rigid-core oligothiophene-S,S-dioxides
AU - Tedesco, E
AU - Della Sala, F
AU - Favaretto, L
AU - Barbarella, G
AU - Albesa, David
AU - Pisignano, D
AU - Gigli, G
AU - Cingolani, R
AU - Harris, Kenneth
PY - 2003/10/8
Y1 - 2003/10/8
N2 - The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene -4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.
AB - The "rigid-core" material 3,5-dimethyl-2,3'-bis(3-methylthiophene)-dithieno[3,2-b:',3'-d]thiophene -4,4-dioxide (DTTOMe4) has the highest photoluminescence ever reported for thiophene-based molecules in the solid state. We report the structure of this material, determined directly from powder X-ray diffraction data using the Genetic Algorithm method for structure solution, followed by Rietveld refinement, and the structural properties are discussed in relation to the structures of the corresponding subsystems DTTO and DTTOMe. While the crystal structures of the latter compounds contain cofacial dimers, the crystal structure of DTTOMe4 comprises layers of molecules aligned in an antiparallel fashion. Intermediate neglect of differential overlap with single configuration interaction (INDO/SCI) calculations on the intermolecular interactions in the three crystal structures show that the different solid-state photoluminescence efficiencies of DTTOMe4, DTTOMe, and DTTO cannot be correlated with the different types of dipole-dipole alignment in the solid state. Instead, photoluminescence efficiencies correlate well with the rate of formation of nonradiatively decaying charge-transfer pairs upon photoexcitation. Because of larger intermolecular distances in DTTOMe4, the photoluminescence is less effectively quenched by charge-transfer processes than in DTTOMe and DTTO.
UR - http://www.scopus.com/inward/record.url?scp=0141957552&partnerID=8YFLogxK
U2 - 10.1021/ja035570o
DO - 10.1021/ja035570o
M3 - Article
C2 - 14519013
SN - 1520-5126
VL - 125
SP - 12277
EP - 12283
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -