Gusev Alexey N, Nemec Ivan, Herchel Radovan, Bayjyyev Eziz, Nyshchimenko Galyna A, Alexandrov Grigory G, Eremenko Igor L, Trávníček Zdeněk, Hasegawa Miki, Linert Wolfgang
General Chemistry Department, Taurida National V.I. Vernadsky University, Simferopol, Ukraine.
Dalton Trans. 2014 May 21;43(19):7153-65. doi: 10.1039/c4dt00462k. Epub 2014 Mar 27.
Nine new mononuclear and polynuclear Cu(II) complexes [Cu(H2L(2))Cl]Cl·3H2O (1), [Cu(H2L(3))Cl]Cl·H2O (2), [Cu(H2L(4))Cl]Cl·2.5H2O (3), Cu3(μ(3)-L(1))2(H2O)32·H2O (4), Cu4(μ-HL(1))48·CH3OH·5H2O (5), Cu2(HL(3))22·2H2O (6a), Cu2(μ-HL(3))22·H2O (6b), Cu2(μ-HL(3))(L(3))Cu(teta)3·2H2O (7) and Cu2(H2L(3))2(ox)2·2H2O·2MeOH (8) containing [5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl]alkanes (H2L(n), n = 1-4) in combination with other ligands, such as chlorido, aqua, triethylenetetramine (teta) and/or oxalato (ox(2-)), were synthesized and characterized by various techniques such as elemental analysis, FTIR, NMR and UV-Vis spectroscopy. X-ray structures of H2L(3) and H2L(4) as well as complexes 1-8 were determined. The X-ray structures revealed that relatively small composition and structural changes in the H2L(n) ligands have a substantial impact on the coordination geometries of the complexes themselves as well as on their resulting magnetic properties. It has been found that the geometries of the complexes vary from square-pyramidal to trigonal-bipyramidal (with τ ranging from 0.00 to 0.96) and, moreover, that the trigonal bipyramidal geometry becomes more preferable with the increase in the length of the polymethylene chain within the corresponding H2L(n) ligand. The magnetic properties of the polynuclear compounds 4, 5, 6, 7 and 8 were analysed using the spin Hamiltonian formalism, which revealed the presence of antiferromagnetic exchange in the polynuclear systems mediated by the title ligands. The significant effect of the geometric parameters on the Cu···Cu exchange interactions in the polynuclear complexes is discussed.
合成了9种新型单核和多核铜（II）配合物[Cu(H2L(2))Cl]Cl·3H2O (1)、[Cu(H2L(3))Cl]Cl·H2O (2)、[Cu(H2L(4))Cl]Cl·2.5H2O (3)、Cu3(μ(3)-L(1))2(H2O)32·H2O (4)、Cu4(μ-HL(1))48·CH3OH·5H2O (5)、Cu2(HL(3))22·2H2O (6a)、Cu2(μ-HL(3))22·H2O (6b)、Cu2(μ-HL(3))(L(3))Cu(teta)3·2H2O (7) 和 Cu2(H2L(3))2(ox)2·2H2O·2MeOH (8)，它们含有[5-(2-吡啶-2-基)-1,2,4-三唑-3-基]烷烃（H2L(n)，n = 1 - 4）并与其他配体如氯、水、三亚乙基四胺（teta）和/或草酸根（ox(2-)）结合，通过元素分析、傅里叶变换红外光谱（FTIR）、核磁共振（NMR）和紫外可见光谱等多种技术对其进行了表征。测定了H2L(3)和H2L(4)以及配合物1 - 8的X射线结构。X射线结构表明，H2L(n)配体中相对较小的组成和结构变化对配合物本身的配位几何结构及其产生的磁性能有重大影响。已发现配合物的几何结构从四方锥到三角双锥不等（τ范围为0.00至0.96），此外，随着相应H2L(n)配体中亚甲基链长度的增加，三角双锥几何结构变得更可取。使用自旋哈密顿形式对多核化合物4、5、6、7和8的磁性能进行了分析，结果表明在由标题配体介导的多核体系中存在反铁磁交换。讨论了几何参数对多核配合物中Cu···Cu交换相互作用的显著影响。
