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Title: Nematic-like stable glasses without equilibrium liquid crystal phases

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4974829· OSTI ID:1465678

In this paper, we report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition. Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. Finally, while itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
SC0002161; DMR-1234320; DMR-1121288
OSTI ID:
1465678
Alternate ID(s):
OSTI ID: 1361753
Journal Information:
Journal of Chemical Physics, Vol. 146, Issue 5; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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Cited By (5)

Vapor-deposited organic glasses exhibit enhanced stability against photodegradation journal January 2018
Generic packing motifs in vapor-deposited glasses of organic semiconductors journal January 2019
Tenfold increase in the photostability of an azobenzene guest in vapor-deposited glass mixtures journal November 2018
Vapor deposition of a nonmesogen prepares highly structured organic glasses journal September 2019
Orientationally ordered glasses via controlled deposition journal October 2019

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