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Title: An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12

Abstract

A structural study of the complex aminated stereotriads, [( tert-butyldimethylsilyl)oxy]-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (1) and its reduced analogue, [( tert-butyldimethylsilyl)oxy]-4-ethenyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (2), revealed a k12-type second-order phase transition in 1 and phase stability of 2 over the temperature range 100–400 K. The observed phase change in 1 has been linked to the partial ordering of the extensive positional disorder of the high temperature phase upon cooling as revealed by single-crystal X-ray diffraction. The ordering breaks the translational symmetry, introduces differences in the molecular volumes of the packed species, and results in a low-temperature crystal structure with Z'=12. The in situ powder X-ray diffraction studies suggest that the transition occurs between 237 K and 180 K upon cooling, but complete amorphization in the range of 244–274 K during heating complicated the assignment of the transition temperature. Lastly, the observed loss of crystallinity has been linked to the phase transition and implies that the loss of long range order is due to the crystallites undergoing the transformation independently from one another.

Authors:
 [1];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Univ. of Wisconsin-Madison, Madison, WI (United States)
OSTI Identifier:
1460085
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Crystal Growth and Design
Additional Journal Information:
Journal Volume: 17; Journal Issue: 11; Journal ID: ISSN 1528-7483
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Vinokur, Anastasiya I., Yakovenko, Andrey, Liu, Lu, Schomaker, Jennifer M., and Guzei, Ilia A. An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12. United States: N. p., 2017. Web. doi:10.1021/acs.cgd.7b01099.
Vinokur, Anastasiya I., Yakovenko, Andrey, Liu, Lu, Schomaker, Jennifer M., & Guzei, Ilia A. An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12. United States. doi:10.1021/acs.cgd.7b01099.
Vinokur, Anastasiya I., Yakovenko, Andrey, Liu, Lu, Schomaker, Jennifer M., and Guzei, Ilia A. Wed . "An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12". United States. doi:10.1021/acs.cgd.7b01099. https://www.osti.gov/servlets/purl/1460085.
@article{osti_1460085,
title = {An Enantiotropic Disorder–Partial Order Solid-State Transformation in a Molecular Solid Involving a Phase with Z' = 12},
author = {Vinokur, Anastasiya I. and Yakovenko, Andrey and Liu, Lu and Schomaker, Jennifer M. and Guzei, Ilia A.},
abstractNote = {A structural study of the complex aminated stereotriads, [(tert-butyldimethylsilyl)oxy]-4-ethynyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (1) and its reduced analogue, [(tert-butyldimethylsilyl)oxy]-4-ethenyl-4-(1-fluorohexyl)-1,2,3-oxathiazocane-2,2-dione (2), revealed a k12-type second-order phase transition in 1 and phase stability of 2 over the temperature range 100–400 K. The observed phase change in 1 has been linked to the partial ordering of the extensive positional disorder of the high temperature phase upon cooling as revealed by single-crystal X-ray diffraction. The ordering breaks the translational symmetry, introduces differences in the molecular volumes of the packed species, and results in a low-temperature crystal structure with Z'=12. The in situ powder X-ray diffraction studies suggest that the transition occurs between 237 K and 180 K upon cooling, but complete amorphization in the range of 244–274 K during heating complicated the assignment of the transition temperature. Lastly, the observed loss of crystallinity has been linked to the phase transition and implies that the loss of long range order is due to the crystallites undergoing the transformation independently from one another.},
doi = {10.1021/acs.cgd.7b01099},
journal = {Crystal Growth and Design},
number = 11,
volume = 17,
place = {United States},
year = {2017},
month = {9}
}

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Figures / Tables:

Figure 1 Figure 1: Crystal structures for selected integer Z$^\prime$ values. The number of high-Z structures falls dramatically above Z$^\prime$= 4.

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