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Entropic Contribution of Flexible Terminals to Mesophase Formation Revealed by Thermodynamic Analysis of 4-Alkyl-4′-isothiocyanatobiphenyl (nTCB)

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Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan, and The Henryk Niewodniczanski Institute of Nuclear Physics, Polish Academy of Sciences, Krakow 31-342, Poland
* Corresponding author. E-mail: [email protected]
†University of Tsukuba.
‡Polish Academy of Sciences.
§Present address: National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.
Cite this: J. Phys. Chem. B 2010, 114, 14, 4870–4875
Publication Date (Web):March 18, 2010
https://doi.org/10.1021/jp100301r
Copyright © 2010 American Chemical Society
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Abstract

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To understand the role of intramolecular degrees of freedom in forming mesophases, thermodynamic analysis was performed for 4-n-alkyl-4′-isothiocyanatobiphenyl (nTCB, n is the number of carbon atoms in the alkyl group), which exhibits the crystal E (CrE) phase as a mesophase. The heat capacities of 2TCB and 5TCB were measured by adiabatic calorimetry. Their entropies of transition (ΔtrsS) were compared with those of other nTCBs (n ≤ 10). ΔtrsS of the phase transition from the ordered crystal to CrE phase increased with their alkyl chain length, whereas that of fusion of the CrE phase remained essentially constant. These behaviors clearly show that the alkyl chain of nTCB is fully disordered even in the CrE phase. Through the comparison of ΔtrsS among 5TCB, 4-pentyl-4′-cyanobiphenyl (5CB), and pentylbiphenyl, the role of the alkyl chain for the formation of mesophases is discussed.

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Standard thermodynamic functions of 2TCB and 5TCB and optimized Cartesian coordinates of all atoms and molecular vibrational frequencies of nTCB (n = 2−5). This material is available free of charge via the Internet at http://pubs.acs.org.

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