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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: [email protected]
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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
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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References

Buss, C. E., Anderson, C. E., Pomije, M. K., Lutz, C. M., Britton, D., and Mann, K. R. (1998). “Structural investigations of vapochromic behavior. X-ray single-crystal and powder diffraction studies of [Pt(CN-iso-C3H7)4][M(CN)4] for M = Pt or Pd.,” J. Am. Chem. Soc. 120, 7783–7790.CrossRefGoogle Scholar
Caliandro, R. and Belviso, B. D. (2014). “RootProf: software for multivariate analysis of unidimensional profiles,” J. Appl. Crystallogr. 47, 1087–1096.CrossRefGoogle Scholar
Chapman, K. W., Lapidus, S. H., and Chupas, P. J. (2015). “Applications of principal component analysis to pair distribution function data,” J. Appl. Crystallogr. 48, 1619–1626.Google Scholar
Daws, C. A., Exstrom, C. L., Sowa, J. R., and Mann, K. R. (1997). “Vapochromic compounds as environmental sensors. 2. Synthesis and nearinfrared and infrared spectroscopy studies of [Pt(arylisonitrile)4]x[Pt(CN)4] upon exposure to volatile organic compounds vapors,” Chem. Mater. 91, 363–368.CrossRefGoogle Scholar
Forniés, J., Fuertes, S., López, J. A., Martín, A., and Sicilia, V. J. (2008). “New water soluble and luminescent platinum(II) compounds, vapochromic behavior of [K(H2O)][Pt(bzq)(CN)2], new examples of the influence of the counterion on the photophysical properties of d8 square-planar complexes,” Inorg. Chem. 47, 7166–7176.Google Scholar
Hammersley, A. P., Svensson, S. O., Hanfland, M., and Hauserman, D. (1996). “Two-dimensional detector software: from real detector to idealised image or two-theta scan,” High Press. Res. 14, 235–248.Google Scholar
Juhás, P., Davis, T., Farrow, C. L., and Billinge, S. J. L. (2013). “PDFgetX3: a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions,” J. Appl. Crystallogr. 46, 560–566.Google Scholar
Kobayashi, A. and Kato, M. (2014). “Vapochromic platinum(II) complexes: crystal engineering toward intelligent sensing devices,” Eur. J. Inorg. Chem. 27, 4469–4483. doi: 10.1002/ejic.201402315.Google Scholar
Rademacher, N., Daemen, L. L., Chronisterc, E. L., and Proffen, T. (2012). “Pair distribution function analysis of molecular compounds: significance and modeling approach discussed using the example of p-terphenyl,” J. Appl. Crystallogr. 45, 482–488.Google Scholar
Wenger, O. S. (2013). “Vapochromism in organometallic and coordination complexes: chemical sensors for volatile organic compounds,” Chem. Rev. 113, 3686–3733.Google Scholar
Wold, S., Esbensen, K., and Geladi, P. (1987). “Principal component analysis,” Chemom. Intell. Lab. Syst. 2, 37–52.Google Scholar