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Supramolecular diversity and magnetic properties of novel heterometallic Cu(II)/Cr(III) complexes prepared from copper powder, Reineckes salt and ethylenediamine |
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| Authors: | Vitalina M Nikitina Vladimir N Kokozay Roman I Zubatyuk Oleg V Shishkin Carlos J Gómez-García Julia Jezierska |
| Institution: | a Department of Inorganic Chemistry, National Taras Shevchenko University, Volodymyrska Street 64, Kyiv 01033, Ukraine b Institute for Scintillation Materials, “Institute for Single Crystals”, National Academy of Sciences of Ukraine, Lenina Avenue 60, Kharkov 61001, Ukraine c Department of Inorganic Chemistry and Technology, Josef Stefan Institute, Jamova 39 1000, Ljubljana, Slovenia d Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, Edificio Institutos de Paterna, 46980, Paterna, Valencia, Spain and Fundación General Universidad de Valencia (FGUV), Spain e Faculty of Chemistry, University of Wroclaw, 14 Joliot-Curie Street, 50-383 Wroclaw, Poland |
| Abstract: | Three novel heterometallic complexes Cu(en)2Cr(NCS)4(NH3)2]Cr(NCS)4(NH3)2] · 6dmf (1), Cu(en)2Cr(NCS)4(NH3)2](OAc) (2) and {Cu(en)2}3{Cr(NCS)4(NH3)2}2(NCS)2](NCS)2 (3) have been synthesized in a one-pot reaction from copper powder, Reineckes salt, NH4X X− = OAc− (2), NCS− (3)] in a dmf (1) or CH3CN (2, 3) solution of ethylenediamine (en). X-ray studies showed that 1 and 2 consist of cationic polymeric chains, formed by  and  building blocks that bridged through thiocyanate anions. In both complexes, distinct hydrogen bonds are present and serve to increase the dimensionality of the compound from one to two (in 1) or three (in 2). The main structural feature of 3 is the pentanuclear Cu3Cr2 cation which is H-bonded with uncoordinated thiocyanate groups generating a 3D supramolecular assembly. The shortest Cu?Cr distances are 5.840(1) Å for 1, 5.856(1) and 6.018(3) Å for 2 and 6.009(9) and 6.465(9) Å for 3. Compounds 1 and 2 are essentially paramagnets whereas compound 3 shows a weak antiferromagnetic coupling. The magnetic properties are simulated and discussed in terms of the structural features. |
| Keywords: | Heterometallic complexes Reineckes anion Copper(II) H-bonds |
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