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Study of the Polymorphism in Copper(II) Decanoate through Its Phase Diagram with Decanoic Acid, and Texture of the Columnar Thermotropic Liquid Crystal Developable Domains in This and Similar Systems

Ramos Riesco, M.; Martinez, Francisco LU ; Rodriguez Cheda, J. A.; Redondo Yelamos, M. I.; Fernandez-Martinez, A. and Lopez-Andres, S. (2015) In Crystal Growth & Design 15(1). p.497-509
Abstract
A new third polymorph of copper(II) decanoate has been found by two methods: from the crystallization of the saltacid solution and from a specific thermal treatment of the polymorph obtained in n-heptane. The new polymorph, whose crystal structure has been solved for the first time, is the most stable from the thermodynamic point of view. It presents a bilayer structure, but with two different types of paddle-wheels catenae with opposite orientations. This polymorphism as well as the temperature vs composition phase diagram of the system, [(1 - x) C9H21CO2H + (x) (C9H21CO2)(2)Cu], were solved by differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, pair distribution function, and optical microscopy.... (More)
A new third polymorph of copper(II) decanoate has been found by two methods: from the crystallization of the saltacid solution and from a specific thermal treatment of the polymorph obtained in n-heptane. The new polymorph, whose crystal structure has been solved for the first time, is the most stable from the thermodynamic point of view. It presents a bilayer structure, but with two different types of paddle-wheels catenae with opposite orientations. This polymorphism as well as the temperature vs composition phase diagram of the system, [(1 - x) C9H21CO2H + (x) (C9H21CO2)(2)Cu], were solved by differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, pair distribution function, and optical microscopy. The singularities of the phase diagram are (a) a Krafft-like process of molecular association of the copper(II) decanoate into the acid solution, at about T = 361.5 K and x = 0.022 (forming salt-acid adducts of 1:1 stoichiometry); (b) a fusion transition as an invariant (T = 379.1 K) of the solid salt in excess from the copper(II) decanoate crystal phase to the discotic liquid crystal, forming homeotropic developable domains (seen for the first time in these systems) of the pure salt into the saturated acid solution. These domains are seen not only in the copper(II) decanoate but also in other members of the series, at high salt concentration in the corresponding acid solution, and allow identification of the hexagonal columnar discotic structure of the mesophase (with the exception of the copper(II) butanoate, where the tetragonal domains with tilted disks, paddle-wheels, were seen in the same salt-acid region). (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Crystal Growth & Design
volume
15
issue
1
pages
497 - 509
publisher
The American Chemical Society
external identifiers
  • wos:000347667500062
  • scopus:84920860133
ISSN
1528-7483
DOI
10.1021/cg501572s
language
English
LU publication?
yes
id
71d9c78a-9db7-40c2-ba21-6c74fc44fa54 (old id 5063113)
date added to LUP
2015-02-25 08:08:28
date last changed
2017-07-30 03:01:15
@article{71d9c78a-9db7-40c2-ba21-6c74fc44fa54,
  abstract     = {A new third polymorph of copper(II) decanoate has been found by two methods: from the crystallization of the saltacid solution and from a specific thermal treatment of the polymorph obtained in n-heptane. The new polymorph, whose crystal structure has been solved for the first time, is the most stable from the thermodynamic point of view. It presents a bilayer structure, but with two different types of paddle-wheels catenae with opposite orientations. This polymorphism as well as the temperature vs composition phase diagram of the system, [(1 - x) C9H21CO2H + (x) (C9H21CO2)(2)Cu], were solved by differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, pair distribution function, and optical microscopy. The singularities of the phase diagram are (a) a Krafft-like process of molecular association of the copper(II) decanoate into the acid solution, at about T = 361.5 K and x = 0.022 (forming salt-acid adducts of 1:1 stoichiometry); (b) a fusion transition as an invariant (T = 379.1 K) of the solid salt in excess from the copper(II) decanoate crystal phase to the discotic liquid crystal, forming homeotropic developable domains (seen for the first time in these systems) of the pure salt into the saturated acid solution. These domains are seen not only in the copper(II) decanoate but also in other members of the series, at high salt concentration in the corresponding acid solution, and allow identification of the hexagonal columnar discotic structure of the mesophase (with the exception of the copper(II) butanoate, where the tetragonal domains with tilted disks, paddle-wheels, were seen in the same salt-acid region).},
  author       = {Ramos Riesco, M. and Martinez, Francisco and Rodriguez Cheda, J. A. and Redondo Yelamos, M. I. and Fernandez-Martinez, A. and Lopez-Andres, S.},
  issn         = {1528-7483},
  language     = {eng},
  number       = {1},
  pages        = {497--509},
  publisher    = {The American Chemical Society},
  series       = {Crystal Growth & Design},
  title        = {Study of the Polymorphism in Copper(II) Decanoate through Its Phase Diagram with Decanoic Acid, and Texture of the Columnar Thermotropic Liquid Crystal Developable Domains in This and Similar Systems},
  url          = {http://dx.doi.org/10.1021/cg501572s},
  volume       = {15},
  year         = {2015},
}