Kaase Dominic, Gotzmann Carla, Rein Stephan, Lan Yanhua, Kacprzak Sylwia, Klingele Julia
Institut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg , Albertstr. 21, D-79104 Freiburg, Germany.
Inorg Chem. 2014 Jun 2;53(11):5546-55. doi: 10.1021/ic500226z. Epub 2014 May 16.
The dinuclear doubly azole-bridged copper(II) complexes Cu(II)2(L)2(MeCN)44·3.73MeCN·0.80H2O and Cu(II)2(L)64·solvent (solvent = 2MeCN·H2O; 2MeCN·2H2O; 1.5MeOH·3.5H2O) were prepared [L = 3-(6-methyl-2-pyridyl)-[1,2,4]triazolo[4,3-a]pyridine]. Structural characterizations revealed very different local geometries about the copper(II) ions, being trigonal bipyramidal for the former (τ = 0.76) and square pyramidal for the latter (τ = 0.07, 0.15, 0.07) complex. Magnetic measurements of bulk material Cu(II)2(L)2(H2O)44 and Cu(II)2(L)64·2H2O revealed antiferromagnetic coupling in both complexes, however, of very different strengths. Electron paramagnetic resonance (EPR) spectroscopy was applied to investigate magnetic properties of the complexes in detail. These experimental findings were supported by broken-symmetry DFT calculations. Systematic magneto-structural correlations are discussed.
制备了双核双唑桥联铜（II）配合物Cu（II）₂(L)₂(MeCN)₄₄·3.73MeCN·0.80H₂O和Cu（II）₂(L)₆₄·溶剂（溶剂 = 2MeCN·H₂O；2MeCN·2H₂O；1.5MeOH·3.5H₂O）[L = 3-(6-甲基-2-吡啶基)-[1,2,4]三唑并[4,3-a]吡啶]。结构表征显示铜（II）离子周围的局部几何结构有很大不同，前者为三角双锥（τ = 0.76），后者为四方锥（τ = 0.07、0.15、0.07）配合物。对块状材料Cu（II）₂(L)₂(H₂O)₄₄和Cu（II）₂(L)₆₄·2H₂O的磁性测量表明，两种配合物均存在反铁磁耦合，然而耦合强度差异很大。应用电子顺磁共振（EPR）光谱详细研究了配合物的磁性。这些实验结果得到了破缺对称性密度泛函理论（DFT）计算的支持。讨论了系统的磁结构相关性。
