Quantitative analysis of intermolecular interactions in orthorhombic rubrene

Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconduct...

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Published in:IUCrJ Vol. 2; no. 5; pp. 563 - 574
Main Authors: Hathwar, Venkatesha R., Sist, Mattia, Jørgensen, Mads R. V., Mamakhel, Aref H., Wang, Xiaoping, Hoffmann, Christina M., Sugimoto, Kunihisa, Overgaard, Jacob, Iversen, Bo Brummerstedt
Format: Journal Article
Language:English
Published: England International Union of Crystallography 01.09.2015
Subjects:
Crystals
Electric properties
Electron configuration
electron density
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
interaction energy
Observations
organic semiconductor
Research Papers
rubrene
Semiconductors
Structure
interaction energy
electron density
organic semiconductor
rubrene
ISSN:2052-2525, 2052-2525
Online Access:Get full text
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Summary:Rubrene is one of the most studied organic semiconductors to date due to its high charge carrier mobility which makes it a potentially applicable compound in modern electronic devices. Previous electronic device characterizations and first principles theoretical calculations assigned the semiconducting properties of rubrene to the presence of a large overlap of the extended π-conjugated core between molecules. We present here the electron density distribution in rubrene at 20 K and at 100 K obtained using a combination of high-resolution X-ray and neutron diffraction data. The topology of the electron density and energies of intermolecular interactions are studied quantitatively. Specifically, the presence of C π ...C π interactions between neighbouring tetracene backbones of the rubrene molecules is experimentally confirmed from a topological analysis of the electron density, Non-Covalent Interaction (NCI) analysis and the calculated interaction energy of molecular dimers. A significant contribution to the lattice energy of the crystal is provided by H—H interactions. The electron density features of H—H bonding, and the interaction energy of molecular dimers connected by H—H interaction clearly demonstrate an importance of these weak interactions in the stabilization of the crystal structure. The quantitative nature of the intermolecular interactions is virtually unchanged between 20 K and 100 K suggesting that any changes in carrier transport at these low temperatures would have a different origin. The obtained experimental results are further supported by theoretical calculations.
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USDOE Office of Science (SC), Basic Energy Sciences (BES)
DNRF93; 2014A0078
ISSN:2052-2525
2052-2525
DOI:10.1107/S2052252515012130