Size Dependence of Nanoscale Confinement on Chiral Transformation

• Published in: Chemistry : a European journal Vol. 16; no. 22; pp. 6482 - 6487
• Main Authors: Wang, Zhigang, Wang, Chunlei, Xiu, Peng, Qi, Wenpeng, Tu, Yusong, Shen, Yumei, Zhou, Ruhong, Zhang, Ruiqin, Fang, Haiping
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 11.06.2010; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Subjects: arenes; Chemistry; chiral transitions; Confinement; Correlation; Crystallography, X-Ray; Dependence; fluorine; Fluorine - chemistry; Models, Molecular; Molecular dynamics; Nanostructure; nanostructures; Nanotechnology; Nanotubes; Nanotubes - chemistry; Orientation; Phenanthrenes - chemistry; Quantum Theory; Simulation; Stereoisomerism; Temperature; Thermodynamics; Transformations
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200903383

Molecular dynamic simulations of the chiral transition of a difluorobenzo[c]phenanthrene molecule (C18H12F2, D molecule) in single‐walled boron‐nitride nanotubes (SWBNNTs) revealed remarkable effects of the nanoscale confinement. The critical temperature, above which the chiral transition occurs, increases considerably with the nanotube diameter, and the chiral transition frequency decreases almost exponentially with respect to the reciprocal of temperature. The chiral transitions correlate closely with the orientational transformations of the D molecule. Furthermore, the interaction energy barriers between the D molecule and the nanotube for different orientational states can characterize the chiral transition. This implies that the temperature threshold of a chiral transition can be controlled by a suitable nanotube. These findings provide new insights to the effect of nanoscale confinement on molecular chirality. Size matters! The chiral transition of difluorobenzo[c]phenanthrene in a boron nitride nanotube occurs under orientation transformation of the molecules from a state parallel to the nanotube axis to a state almost perpendicular to the nanotube axis. Furthermore, the interactions between the chiral molecule and the nanochannel can characterize the chiral transition between these two conformational states.