Rubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state
KAUST DepartmentKAUST Solar Center (KSC)
Laboratory for Computational and Theoretical Chemistry of Advanced Materials
Material Science and Engineering Program
Physical Science and Engineering (PSE) Division
Online Publication Date2015-07-02
Print Publication Date2015-07-15
Permanent link to this recordhttp://hdl.handle.net/10754/558300
MetadataShow full item record
AbstractRubrene is one of the most studied molecular semiconductors; its chemical structure consists of a tetracene backbone with four phenyl rings appended to the two central fused rings. Derivatization of these phenyl rings can lead to two very different solid-state molecular conformations and packings: One in which the tetracene core is planar and there exists substantive overlap among neighboring π-conjugated backbones; and another where the tetracene core is twisted and the overlap of neighboring π-conjugated backbones is completely disrupted. State-of-the-art electronic-structure calculations show for all isolated rubrene derivatives that the twisted conformation is more favorable (by -1.7 to -4.1 kcal mol-1), which is a consequence of energetically unfavorable exchange-repulsion interactions among the phenyl side groups. Calculations based on available crystallographic structures reveal that planar conformations of the tetracene core in the solid state result from intermolecular interactions that can be tuned through well-chosen functionalization of the phenyl side groups, and lead to improved intermolecular electronic couplings. Understanding the interplay of these intramolecular and intermolecular interactions provides insight into how to chemically modify rubrene and similar molecular semiconductors to improve the intrinsic materials electronic properties.
CitationRubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state 2015:150615105527002 Journal of the American Chemical Society
PublisherAmerican Chemical Society (ACS)
- Quantitative analysis of intermolecular interactions in orthorhombic rubrene.
- Authors: Hathwar VR, Sist M, Jørgensen MR, Mamakhel AH, Wang X, Hoffmann CM, Sugimoto K, Overgaard J, Iversen BB
- Issue date: 2015 Sep 1
- Optical spectra obtained from amorphous films of rubrene: Evidence for predominance of twisted isomer.
- Authors: Kytka M, Gisslen L, Gerlach A, Heinemeyer U, Kovác J, Scholz R, Schreiber F
- Issue date: 2009 Jun 7
- Synthesis of BN-fused polycyclic aromatics via tandem intramolecular electrophilic arene borylation.
- Authors: Hatakeyama T, Hashimoto S, Seki S, Nakamura M
- Issue date: 2011 Nov 23
- A DFT study on the photoelectric properties of rubrene and its derivatives.
- Authors: Zhang M, Hua Z, Liu W, Liu H, He S, Zhu C, Zhu Y
- Issue date: 2020 Jan 22
- Accurate calculation of transport properties for organic molecular semiconductors with spin-component scaled MP2 and modern density functional theory methods.
- Authors: Sancho-García JC, Pérez-Jiménez AJ
- Issue date: 2008 Jul 14