Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Chile.
J Mol Model. 2013 Jul;19(7):2835-44. doi: 10.1007/s00894-012-1696-5. Epub 2012 Dec 7.
A theoretical study of the magnetic properties, using density functional theory, of a family of trinuclear μ3-OH copper(II) complexes reported in the literature is presented. The reported X-ray crystal structures of Cu3(μ3-OH)(aat)3(H2O)32 · H2O (HUKDUM), where aat: 3-acetylamine-1,2,4-triazole; [Cu3(μ3-OH)(aaat)3(H2SO4)(HSO4)(H2O)] (HUKDOG), where aaat: 3-acetylamine-5-amine-1,2,4-triazole; [Cu3(μ3-OH)(PhPyCNO)3(tchlphac)2] (HOHQUR), where PhPyCNO: phenyl 2-pyridyl-ketoxime and tchlphac: acid 2,4,5-trichlorophenoxyacetic; [Cu3(μ3-OH)(PhPyCNO)3(NO3)2(CH3OH)] (ILEGEM); [Cu3(μ3-OH)(pz)3(Hpz)3(ClO4)2] (QOPJIP), where Hpz = pyrazole; [Cu3(μ3-OH)(pz)3(Hpz)(Me3CCOO)2] ∙ 2Me3CCOOH (DEFSEN) and [Cu3(μ3-OH)(8-amino-4-methyl-5-azaoct-3-en-2-one)3][CuI3] (RITXUO), were used in the calculations. The magnetic exchange constants were calculated using the broken-symmetry approach. The calculated J values are for HUKDUM J1 = -68.6 cm(-1), J2 = -69.9 cm(-1), J3 = -70.4 cm(-1); for HUKDOG, J1 = -73.5 cm(-1), J2 = -58.9 cm(-1), J3 = -62.1 cm(-1); for HOHQUR J1 = -128.3 cm(-1), J2 = -134.1 cm(-1), J3 = -120.4 cm(-1); for ILEGEM J1 = -151.6 cm(-1), J2 = -173.9 cm(-1), J3 = -186.9 cm(-1); for QOPJIP J1 = -118.3 cm(-1), J2 = -106.0 cm(-1), J3 = -120.6 cm(-1); for DEFSEN J1 = -74.9 cm(-1), J2 = -64.0 cm(-1), J3 = -57.7 cm(-1) and for RITXUO J1 = -10.9 cm(-1), J2 = +14.3 cm(-1), J3 = -35.4 cm(-1). The Kahn-Briat model was used to correlate the calculated magnetic properties with the overlap of the magnetic orbitals. Spin density surfaces show that the delocalization mechanism is predominant in all the studied compounds.
本文运用密度泛函理论对文献中报道的一组三聚体 μ3-OH 铜（II）配合物的磁性性质进行了理论研究。报道的 Cu3(μ3-OH)(aat)3(H2O)32·H2O（HUKDUM）、[Cu3(μ3-OH)(aaat)3(H2SO4)(HSO4)(H2O)]（HUKDOG）、[Cu3(μ3-OH)(PhPyCNO)3(tchlphac)2]（HOHQUR）、[Cu3(μ3-OH)(PhPyCNO)3(NO3)2(CH3OH)]（ILEGEM）、[Cu3(μ3-OH)(pz)3(Hpz)3(ClO4)2]（QOPJIP）、[Cu3(μ3-OH)(pz)3(Hpz)(Me3CCOO)2]·2Me3CCOOH（DEFSEN）和[Cu3(μ3-OH)(8-氨基-4-甲基-5-氮杂辛-3-烯-2-酮)3][CuI3]（RITXUO）的晶体结构被用于计算。使用破对称方法计算了磁交换常数。计算得到的 J 值分别为 HUKDUM 的 J1=-68.6cm-1，J2=-69.9cm-1，J3=-70.4cm-1；HUKDOG 的 J1=-73.5cm-1，J2=-58.9cm-1，J3=-62.1cm-1；HOHQUR 的 J1=-128.3cm-1，J2=-134.1cm-1，J3=-120.4cm-1；ILEGEM 的 J1=-151.6cm-1，J2=-173.9cm-1，J3=-186.9cm-1；QOPJIP 的 J1=-118.3cm-1，J2=-106.0cm-1，J3=-120.6cm-1；DEFSEN 的 J1=-74.9cm-1，J2=-64.0cm-1，J3=-57.7cm-1；RITXUO 的 J1=-10.9cm-1，J2=+14.3cm-1，J3=-35.4cm-1。Kahn-Briat 模型用于将计算得到的磁性性质与磁轨道的重叠相关联。自旋密度曲面表明，在所有研究的化合物中，离域机制是主要的。
