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Dynamic characterization of structural changes in vapochromic compounds by pair distribution function

Published online by Cambridge University Press:  28 February 2017

R. Caliandro Open the ORCID record for R. Caliandro [Opens in a new window] ,
B. D. Belviso ,
C. Cuocci ,
S. Fuertes ,
V. Sicilia ,
J. C. Hanson ,
G. Tutuncu ,
E. Doorhyee  and
A. Altomare
R. Caliandro*
Affiliation:
Institute of Crystallography, CNR, Bari, Italy
B. D. Belviso
Affiliation:
Institute of Crystallography, CNR, Bari, Italy
C. Cuocci
Affiliation:
Institute of Crystallography, CNR, Bari, Italy
S. Fuertes
Affiliation:
Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC, Zaragoza, Spain
V. Sicilia
Affiliation:
Departamento de Química Inorgánica, Universidad de Zaragoza-CSIC, Zaragoza, Spain
J. C. Hanson
Affiliation:
Chemistry Department, Brookhaven National Laboratory, New York
G. Tutuncu
Affiliation:
NSLS II, Photon Science Division, Brookhaven National Laboratory, New York
E. Doorhyee
Affiliation:
NSLS II, Photon Science Division, Brookhaven National Laboratory, New York
A. Altomare
Affiliation:
Institute of Crystallography, CNR, Bari, Italy
*
a)Author to whom correspondence should be addressed. Electronic mail: rocco.caliandro@ic.cnr.it
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Abstract

Two examples of anionic complexes having vapochromic behavior are investigated: [K(H2O)][Pt(ppy)(CN)2] “Pt(ppy)” and [K(H2O)][Pt(bzq)(CN)2] “Pt(bzq)”, where ppy = 2-phenylpyridinate and bzq = 7,8-benzoquinolate. These monohydrate-potassium salts exhibit a change in color from purple to yellow [Pt(ppy)] and from red to yellow [Pt(bzq)] upon heating to 110 °C, and they transform back into the original color upon absorption of water molecules from the environment. Available only in the form of polycrystalline samples, no structural information on such compounds is accessible, due to highly overlapping peaks in powder diffraction profiles. We use in situ Pair Distribution Function measurements on powder samples to investigate the dynamics of the structural changes induced by temperature variations. By means of a multivariate approach, we were able to extract dynamic structural information from collected profiles without using prior knowledge on the static crystal structure of the compounds. The critical temperature and the characteristics of the vapochromic transition have been identified, as well as the main structural changes causing it.

Keywords

vapochromic compoundsstructural transitionspair distribution functionmultivariate analysis

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Type
Technical Articles
Information
Powder Diffraction , Volume 32 , Supplement S1 , September 2017 , pp. S118 - S122
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Copyright
Copyright © International Centre for Diffraction Data 2017 

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