Simulation of Crystallization of Pentacene and Its Derivatives from Solution

• Published in: Journal of physical chemistry. C 2021-02, Vol.125 (4), p.2257-2263
• Main Author: Yoneya, Makoto
• Format: Article
• Language: English
• Subjects: C: Energy Conversion and Storage
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/acs.jpcc.0c09842

The order-emerging stage of crystallization in solution of pentacene and its derivatives was investigated using molecular dynamics simulations. Spontaneous formation of the layered herringbone motif of the pentacene crystal was successfully demonstrated starting from a random mixed solution state. Moreover, I found that the formation of the layer order and the in-layer herringbone-order occurred simultaneously in my simulation because the formation of the layer was driven by the edge-to-face (herringbone shape) interaction between pentacene molecules. This is markedly different from the stepwise order formation from the liquid-crystal-like layer order to the subsequent in-layer herringbone order in the corresponding simulation of the dialkylated pentacene derivative 2,9-dioctyl-pentacene. I also demonstrated the change in the crystal motif from herringbone for pentacene to face-to-face π-stacking for the dechlorinated pentacene derivative 6,13-dichloropentacene because of the steric effect of substituted chlorines disabling the edge-to-face intermolecular interaction in nonsubstituted pentacene.