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Title: Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P{sub 4}Se{sub 3} and CuX (X=Cl, Br, I)

Abstract

The formation of coordination polymers (CuCl)P{sub 4}Se{sub 3} (1), (CuBr){sub 3}(P{sub 4}Se{sub 3}){sub 2} (2), (CuI){sub 3}(P{sub 4}Se{sub 3}){sub 2} (3) and (CuI)P{sub 4}Se{sub 3} (4), from solutions of copper(I) halides and P{sub 4}Se{sub 3} by diffusion methods has been studied. The new compounds were characterized by X-ray crystallography, solid-state {sup 31}P MAS NMR and Raman spectroscopy. Theoretical studies on the DFT level in the crystalline phase allowed the unequivocal assignment of the recorded Raman shifts between 200 and 480 cm{sup -1}. The structure of 1 consists of a 2D network of castellated [CuCl]{sub n} chains and bidentate P{sub 4}Se{sub 3} molecules. The 3D network of 2 comprises [CuBr]{sub n} chains, which are linked by tridentate P{sub 4}Se{sub 3} molecules. Compound 3 is a three-dimensional polymer composed of four-membered (CuI){sub 2} rings and castellated [CuI]{sub n} chains, which are linked by tridentate P{sub 4}Se{sub 3} molecules involving two basal and the apical P atoms. Thermal conversion of 1 at 230 deg. C gives (CuCl){sub 3}(P{sub 4}Se{sub 3}){sub 2} (5), which is isostructural with 2. The thermal conversion of (CuI){sub 3}P{sub 4}S{sub 3}, which was studied for comparison gave at 371 deg. C (CuI){sub 3}P{sub 4}S{sub 4}, Cu{sub 3}PS{sub 4} andmore » small amounts of Cu{sub 6}PS{sub 5}I. - Graphical Abstract: New coordination polymers have been prepared and characterized by the reaction of P{sub 4}Se{sub 3} and copper(I) halides solutions under diffusion conditions. Highlights: > Coordination polymers from P{sub 4}Se{sub 3} and copper(I) halide are described. > Solid-state phases are prepared from solution by interdiffusion techniques. > One-, two- and three-dimensional polymers are formed. > Up to three P atoms are involved in coordination to copper. > Application of {sup 31}P MAS NMR spectroscopy.« less

Authors:
 [1]; ;  [2];  [1];  [1]; ;  [1]
  1. Institut fuer Anorganische Chemie der Universitaet Regensburg, 93040 Regensburg (Germany)
  2. Institut fuer Biophysik und Physikalische Biochemie der Universitaet Regensburg, 93040 Regensburg (Germany)
Publication Date:
OSTI Identifier:
21580137
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 184; Journal Issue: 7; Other Information: DOI: 10.1016/j.jssc.2011.05.011; PII: S0022-4596(11)00260-X; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER; COPPER BROMIDES; COPPER CHLORIDES; COPPER IODIDES; CRYSTALLOGRAPHY; MOLECULES; NUCLEAR MAGNETIC RESONANCE; PHOSPHORUS; PHOSPHORUS 31; POLYMERS; RAMAN SPECTRA; RAMAN SPECTROSCOPY; SOLIDS; SOLUTIONS; THREE-DIMENSIONAL CALCULATIONS; X RADIATION; BROMIDES; BROMINE COMPOUNDS; CHLORIDES; CHLORINE COMPOUNDS; COPPER COMPOUNDS; COPPER HALIDES; DISPERSIONS; ELECTROMAGNETIC RADIATION; ELEMENTS; HALIDES; HALOGEN COMPOUNDS; HOMOGENEOUS MIXTURES; IODIDES; IODINE COMPOUNDS; IONIZING RADIATIONS; ISOTOPES; LASER SPECTROSCOPY; LIGHT NUCLEI; MAGNETIC RESONANCE; METALS; MIXTURES; NONMETALS; NUCLEI; ODD-EVEN NUCLEI; PHOSPHORUS ISOTOPES; RADIATIONS; RESONANCE; SPECTRA; SPECTROSCOPY; STABLE ISOTOPES; TRANSITION ELEMENT COMPOUNDS; TRANSITION ELEMENTS

Citation Formats

Biegerl, Andreas, Groeger, Christian, Kalbitzer, Hans R., Pfitzner, Arno, Wachter, Joachim, E-mail: Joachim.Wachter@chemie.uni-regensburg.de, Weihrich, Richard, and Zabel, Manfred. Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P{sub 4}Se{sub 3} and CuX (X=Cl, Br, I). United States: N. p., 2011. Web. doi:10.1016/j.jssc.2011.05.011.
Biegerl, Andreas, Groeger, Christian, Kalbitzer, Hans R., Pfitzner, Arno, Wachter, Joachim, E-mail: Joachim.Wachter@chemie.uni-regensburg.de, Weihrich, Richard, & Zabel, Manfred. Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P{sub 4}Se{sub 3} and CuX (X=Cl, Br, I). United States. doi:10.1016/j.jssc.2011.05.011.
Biegerl, Andreas, Groeger, Christian, Kalbitzer, Hans R., Pfitzner, Arno, Wachter, Joachim, E-mail: Joachim.Wachter@chemie.uni-regensburg.de, Weihrich, Richard, and Zabel, Manfred. Fri . "Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P{sub 4}Se{sub 3} and CuX (X=Cl, Br, I)". United States. doi:10.1016/j.jssc.2011.05.011.
@article{osti_21580137,
title = {Structures, spectroscopic studies and solid-state thermal transformations of coordination polymers from P{sub 4}Se{sub 3} and CuX (X=Cl, Br, I)},
author = {Biegerl, Andreas and Groeger, Christian and Kalbitzer, Hans R. and Pfitzner, Arno and Wachter, Joachim, E-mail: Joachim.Wachter@chemie.uni-regensburg.de and Weihrich, Richard and Zabel, Manfred},
abstractNote = {The formation of coordination polymers (CuCl)P{sub 4}Se{sub 3} (1), (CuBr){sub 3}(P{sub 4}Se{sub 3}){sub 2} (2), (CuI){sub 3}(P{sub 4}Se{sub 3}){sub 2} (3) and (CuI)P{sub 4}Se{sub 3} (4), from solutions of copper(I) halides and P{sub 4}Se{sub 3} by diffusion methods has been studied. The new compounds were characterized by X-ray crystallography, solid-state {sup 31}P MAS NMR and Raman spectroscopy. Theoretical studies on the DFT level in the crystalline phase allowed the unequivocal assignment of the recorded Raman shifts between 200 and 480 cm{sup -1}. The structure of 1 consists of a 2D network of castellated [CuCl]{sub n} chains and bidentate P{sub 4}Se{sub 3} molecules. The 3D network of 2 comprises [CuBr]{sub n} chains, which are linked by tridentate P{sub 4}Se{sub 3} molecules. Compound 3 is a three-dimensional polymer composed of four-membered (CuI){sub 2} rings and castellated [CuI]{sub n} chains, which are linked by tridentate P{sub 4}Se{sub 3} molecules involving two basal and the apical P atoms. Thermal conversion of 1 at 230 deg. C gives (CuCl){sub 3}(P{sub 4}Se{sub 3}){sub 2} (5), which is isostructural with 2. The thermal conversion of (CuI){sub 3}P{sub 4}S{sub 3}, which was studied for comparison gave at 371 deg. C (CuI){sub 3}P{sub 4}S{sub 4}, Cu{sub 3}PS{sub 4} and small amounts of Cu{sub 6}PS{sub 5}I. - Graphical Abstract: New coordination polymers have been prepared and characterized by the reaction of P{sub 4}Se{sub 3} and copper(I) halides solutions under diffusion conditions. Highlights: > Coordination polymers from P{sub 4}Se{sub 3} and copper(I) halide are described. > Solid-state phases are prepared from solution by interdiffusion techniques. > One-, two- and three-dimensional polymers are formed. > Up to three P atoms are involved in coordination to copper. > Application of {sup 31}P MAS NMR spectroscopy.},
doi = {10.1016/j.jssc.2011.05.011},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 7,
volume = 184,
place = {United States},
year = {2011},
month = {7}
}