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Energetic and Structural Insights into the Molecular and Supramolecular Properties of Rubrene
Author(s) -
Lima Carlos F. R. A. C.,
Costa José C. S.,
Lima Luís M. Spencer S.,
Melo André,
Silva Artur M. S.,
Santos Luís M. N. B. F.
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201601636
Subject(s) - rubrene , tetracene , dimer , supramolecular chemistry , intermolecular force , chemistry , chemical physics , anthracene , crystallography , materials science , crystal structure , computational chemistry , molecule , photochemistry , organic chemistry
The molecular and supramolecular structure and energetics of tetracene and rubrene were investigated by a combined experimental and theoretical study. Accurate equilibrium vapour pressures at various temperatures were measured for both compounds. For rubrene the energetic analysis evidences lower crystal packing efficiency, strong molecular destabilization and confirms the non‐planar twisted equilibrium structure in the gas phase. The results also indicate that phenyl internal rotation in rubrene is highly hindered. The intra‐ and intermolecular interactions in crystal tetracene and rubrene were evaluated by computational methods. The representative stacked dimer of the tetracene⋅⋅⋅tetracene interaction in rubrene has lower ionization energy than the one modelling the same interaction in tetracene, due to stronger cation⋅⋅⋅π interactions in the cation‐radical of rubrene. Charge distribution in the cation dimer is symmetrical in rubrene, whereas in tetracene it is largely localized on the C−H⋅⋅⋅π donor partner of the herringbone dimer. These findings highlight the impact of cation⋅⋅⋅π interactions on the semiconducting properties of OSCs.