Rubrene: The interplay between intramolecular and intermolecular interactions determines the planarization of its tetracene core in the solid state
Type
ArticleKAUST Department
KAUST Solar Center (KSC)Laboratory for Computational and Theoretical Chemistry of Advanced Materials
Material Science and Engineering Program
Physical Science and Engineering (PSE) Division
Date
2015-07-02Online Publication Date
2015-07-02Print Publication Date
2015-07-15Permanent link to this record
http://hdl.handle.net/10754/558300
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Show full item recordAbstract
Rubrene 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.Citation
Rubrene: 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 SocietyPublisher
American Chemical Society (ACS)PubMed ID
26075966Additional Links
http://pubs.acs.org/doi/abs/10.1021/jacs.5b04066ae974a485f413a2113503eed53cd6c53
10.1021/jacs.5b04066
Scopus Count
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