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

Journal Article · Fri Jul 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.05.011· OSTI ID:21580137

Biegerl, Andreas ^[1]; Groeger, Christian; Kalbitzer, Hans R ^[2]; Pfitzner, Arno ^[1]; Wachter, Joachim ^[1]; Weihrich, Richard; Zabel, Manfred ^[1]

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1. Institut fuer Anorganische Chemie der Universitaet Regensburg, 93040 Regensburg (Germany)
2. Institut fuer Biophysik und Physikalische Biochemie der Universitaet Regensburg, 93040 Regensburg (Germany)

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.

• OSTI ID: 21580137
• Journal Information: Journal of Solid State Chemistry, Vol. 184, 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.; ISSN 0022-4596
• Country of Publication: United States
• Language: English

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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
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COPPER HALIDES
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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
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SPECTRA
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