Spectroscopic and Thermal Analyses of Ortho-Benzylphenol Crystalline Polymorphism

J. Baran; N. A. Davydova; M. Drozd; E. A. Ponezha; V. Ya. Reznichenko

doi:10.15407/ujpe63.2.95

Spectroscopic and Thermal Analyses of Ortho-Benzylphenol Crystalline Polymorphism

Authors

J. Baran Institute of Low Temperature and Structure Research, PAS
N. A. Davydova Institute of Physics, Nat. Acad. of Sci. of Ukraine
M. Drozd Institute of Low Temperature and Structure Research, PAS
E. A. Ponezha Bogolyubov Institute for Theoretical Physics, Nat. Acad. of Sci. of Ukraine
V. Ya. Reznichenko Institute of Physics, Nat. Acad. of Sci. of Ukraine

DOI:

https://doi.org/10.15407/ujpe63.2.95

Keywords:

infrared spectroscopy, conformers, ortho-benzylphenol

Abstract

In situ, we present the experimental spectroscopic proof of the existence of polymorphism in ortho-benzylphenol. Infrared spectroscopy was used for the first time to investigate the structural changes during the crystallization of a metastable phase, which is transformed, in the course of time, into a stable one. The results show that, in the stable and metastable phases, different conformers of ortho-benzylphenol molecule predominate, which differ in the orientation of the aromatic rings relative to the connecting methylene bridge. Namely, it is shown that the transformation of the metastable phase into a stable one is accompanied by the rotation of the OH-substituted aromatic ring relative to the connecting methylene bridge from 59.9∘ to 180.0∘ in the molecule of ortho-benzylphenol. The DSC experiment has shown that the process of nucleation of a metastable phase preferentially develops below ∼1.1 Tg (243 K), the crystallization occurs at ∼272 K, and the melting happens at 290.2 K. The difference in the temperature regions of nucleation and crystallization explains a good glass-forming status of ortho-benzylphenol.

References

<ol>
<li>S. Katsyuba, A. Chernova, R. Schmutzler. Vibrational spectra and conformational isomerism of calixarene building blocks: 2-benzylphenol. Org. Biomol. Chem. 1, 714 (2003).
<a href="https://doi.org/10.1039/b211164k">https://doi.org/10.1039/b211164k</a>
</li>
<li>J.C. Bryan, L.H. Delmau, J.B. Nicholas, L.M. Rogers, R.D. Rogers, B.A. Moyer. Cesium recognition by supramolecular assemblies of 2-benzylphenol and 2-benzylphenolate. Struct. Chem. 10, 187 (1999).
<a href="https://doi.org/10.1023/A:1021884429538">https://doi.org/10.1023/A:1021884429538</a>
</li>
<li>L. McMaster, W.M. Bruner. Benzylation of phenol. Ind. Eng. Chem. 28, 505 (1936).
<a href="https://doi.org/10.1021/ie50316a036">https://doi.org/10.1021/ie50316a036</a>
</li>
<li>J.J. Moura Ramos, S. Rocha, H.P. Diogo. Polymorphic forms of o-benzylphenol and slow molecular motions in the amorphous state. J. Non-Cryst. Solids 344, 119 (2004).
<a href="https://doi.org/10.1016/j.jnoncrysol.2004.07.061">https://doi.org/10.1016/j.jnoncrysol.2004.07.061</a>
</li>
<li>F. Paladi, M. Oguni. Anomalous generation and extinction of crystal nuclei in nonequilibrium supercooled liquid o-ben-zylphenol. Phys. Rev. B 65, 144202 (2002).
<a href="https://doi.org/10.1103/PhysRevB.65.144202">https://doi.org/10.1103/PhysRevB.65.144202</a>
</li>
<li>J. Baran, N.A. Davydova, M. Drozd, A. Pietraszko. Experimental evidence of formation of a new phase in supercooled liquid 2-biphenylmethanol. J. Phys.: Condens. Matter 18, 5695 (2006).
<a href="https://doi.org/10.1088/0953-8984/18/24/010">https://doi.org/10.1088/0953-8984/18/24/010</a>
</li>
<li>J. Baran, N.A. Davydova, M. Drozd. The role of nucleation in vitrification of supercooled liquids. J. Phys.: Condens. Matter 22, 155108 (2010).
<a href="https://doi.org/10.1088/0953-8984/22/15/155108">https://doi.org/10.1088/0953-8984/22/15/155108</a>
</li>
<li>J. Baran, N.A. Davydova, M. Drozd. Discovery of a new polymorphic phase of ortho-bromobenzophenone. Chem. Phys. Lett. 621, 18 (2015).
<a href="https://doi.org/10.1016/j.cplett.2014.12.041">https://doi.org/10.1016/j.cplett.2014.12.041</a>
</li>
<li>V.N. Novikov, A.P. Sokolov. Universality of the dynamic crossover in glass-forming liquids: A "magic" relaxation time. Phys. Rev. E 67, 031507 (2003).
<a href="https://doi.org/10.1103/PhysRevE.67.031507">https://doi.org/10.1103/PhysRevE.67.031507</a></li></ol>

Downloads

Published

2018-03-02

How to Cite

Baran, J., Davydova, N. A., Drozd, M., Ponezha, E. A., & Reznichenko, V. Y. (2018). Spectroscopic and Thermal Analyses of Ortho-Benzylphenol Crystalline Polymorphism. Ukrainian Journal of Physics, 63(2), 95. https://doi.org/10.15407/ujpe63.2.95

Download Citation

Issue

Vol. 63 No. 2 (2018)

Section

Optics, atoms and molecules

License

Copyright Agreement
License to Publish the Paper
Kyiv, Ukraine

The corresponding author and the co-authors (hereon referred to as the Author(s)) of the paper being submitted to the Ukrainian Journal of Physics (hereon referred to as the Paper) from one side and the Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, represented by its Director (hereon referred to as the Publisher) from the other side have come to the following Agreement:

1. Subject of the Agreement.
The Author(s) grant(s) the Publisher the free non-exclusive right to use the Paper (of scientific, technical, or any other content) according to the terms and conditions defined by this Agreement.

2. The ways of using the Paper.
2.1. The Author(s) grant(s) the Publisher the right to use the Paper as follows.
2.1.1. To publish the Paper in the Ukrainian Journal of Physics (hereon referred to as the Journal) in original language and translated into English (the copy of the Paper approved by the Author(s) and the Publisher and accepted for publication is a constitutive part of this License Agreement).
2.1.2. To edit, adapt, and correct the Paper by approval of the Author(s).
2.1.3. To translate the Paper in the case when the Paper is written in a language different from that adopted in the Journal.
2.2. If the Author(s) has(ve) an intent to use the Paper in any other way, e.g., to publish the translated version of the Paper (except for the case defined by Section 2.1.3 of this Agreement), to post the full Paper or any its part on the web, to publish the Paper in any other editions, to include the Paper or any its part in other collections, anthologies, encyclopaedias, etc., the Author(s) should get a written permission from the Publisher.

3. License territory.
The Author(s) grant(s) the Publisher the right to use the Paper as regulated by sections 2.1.1–2.1.3 of this Agreement on the territory of Ukraine and to distribute the Paper as indispensable part of the Journal on the territory of Ukraine and other countries by means of subscription, sales, and free transfer to a third party.

4. Duration.
4.1. This Agreement is valid starting from the date of signature and acts for the entire period of the existence of the Journal.

5. Loyalty.
5.1. The Author(s) warrant(s) the Publisher that:
– he/she is the true author (co-author) of the Paper;
– copyright on the Paper was not transferred to any other party;
– the Paper has never been published before and will not be published in any other media before it is published by the Publisher (see also section 2.2);
– the Author(s) do(es) not violate any intellectual property right of other parties. If the Paper includes some materials of other parties, except for citations whose length is regulated by the scientific, informational, or critical character of the Paper, the use of such materials is in compliance with the regulations of the international law and the law of Ukraine.

6. Requisites and signatures of the Parties.
Publisher: Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine.
Address: Ukraine, Kyiv, Metrolohichna Str. 14-b.
Author: Electronic signature on behalf and with endorsement of all co-authors.