TY  - JOUR
A1  - Farra, Ramzi
A1  - Thiel, Kerstin
A1  - Winter, Alette
A1  - Klamroth, Tillmann
A1  - Poeppl, Andreas
A1  - Kelling, Alexandra
A1  - Schilde, Uwe
A1  - Taubert, Andreas
A1  - Strauch, Peter
T1  - Tetrahalidocuprates(II)-structure and EPR spectroscopy Part 1: Tetrabromidocuprates(II)
T2  - New journal of chemistry
N2  - Tetrahalidocuprates(II) show a high degree of structural flexibility. We present the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of four new tetrabromidocuprate(II) compounds and compare the results with previously reported data. The cations in the new compounds are the sterically demanding benzyltriphenylphosphonium, methyltriphenylphosphonium, tetraphenylphosphonium, and hexadecyltrimethylammonium ions; they were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. X-Ray crystallography shows that in all four complexes the [CuBr4](2-) units have a distorted tetrahedral coordination geometry which is in agreement with DFT calculations. The EPR hyperfine structure was not resolved. This is due to the exchange broadening resulting from still incomplete separation of the paramagnetic Cu(II) centres. Nevertheless, the principal values of the electron Zeemann tensor (g(parallel to) and g(perpendicular to)) of the complexes could be determined. A correlation of structural (X-ray) parameters with the spin density at the copper centres (DFT) is well reflected in the EPR spectra of the bromidocuprates. This enables the correlation of X-ray and EPR parameters to predict the structure of tetrabromidocuprates in physical states other than the crystalline state. As a result, we provide a method to structurally characterize [CuBr4](2-) in, for example, ionic liquids or in solution, which has important implications for e.g. catalysis or materials science.
Y1  - 2011
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/37095
SN  - 1144-0546
VL  - 35
IS  - 12
SP  - 2793
EP  - 2803
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  -