Ferromagnetic interactions in EO-azido-bridged binuclear transition metal(Ⅱ) systems: Syntheses, crystal structures and magnetostructural correlations  

作　　者：ZHANG ShiYuan WANG BingWu XU Na SHI Wei GAO Song CHENG Peng 

机构地区：[1]Key Laboratory of Advanced Energy Materials Chemistry (MOE) Department of Chemistry, Nankai University [2]Beijing National Laboratory for Molecular Sciences, Beijing 100190, China [3]State Key Lab of Rare Earth Materials Chemistry and Applications College of Chemistry and Molecular Engineering, Peking University Beijing 100871, China

出　　处：《Science China Chemistry》2012年第6期942-950,共9页中国科学（化学英文版）

基　　金：supported by grants from the National Natural Science Foundation of China (90922032, 21171100, 21151001);Ministry of Education (IRT0927)

摘　　要：Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis（3-（pyridin-2-yl）-lH-pyrazol-1- yl）ethane （bppe）, formulated as [M2（N3）2（bppe）2]（C104）2 （M = Co, 1; Ni, 2; Cu, 3）, were successfully synthesized. They were structurally and magnetically characterized. In 1-3, the double azido ions link two adjacent octahedral metal centers together in the end-to-on mode （EO）, with the M-NEo-M angles of 99.41°, 100.24° and 99.80°, respectively. The co-ligand bppe acts as terminal ligand to saturate the remaining coordination sites. The magnetic properties of 1-3 have been investigated in the tem- perature range of 2-300 K. Fitting of the magnetic susceptibility data revealed the occurrence of the strong ferromagnetic in- teractions [J = 26.32 cm-1 （1）, J = 38.23 cm-1 （2） and J = 139.83 cm-1 （3）]. Density functional theory calculations have been performed on 1-3 to provide a magneto-structural correlation of the ferromagnetic behavior.Three new isostructural binuclear transition metal complexes with azido ion and 1,2-bis(3-(pyridin-2-yl)-1H-pyrazol-1-yl)ethane (bppe), formulated as [M 2 (N 3 ) 2 (bppe) 2 ](ClO 4 ) 2 (M = Co, 1; Ni, 2; Cu, 3), were successfully synthesized. They were structurally and magnetically characterized. In 1-3, the double azido ions link two adjacent octahedral metal centers together in the end-to-on mode (EO), with the M-N EO -M angles of 99.41°, 100.24° and 99.80°, respectively. The co-ligand bppe acts as terminal ligand to saturate the remaining coordination sites. The magnetic properties of 1-3 have been investigated in the temperature range of 2-300 K. Fitting of the magnetic susceptibility data revealed the occurrence of the strong ferromagnetic interactions [J = 26.32 cm-1 (1), J = 38.23 cm-1 (2) and J = 139.83 cm-1 (3)]. Density functional theory calculations have been performed on 1-3 to provide a magneto-structural correlation of the ferromagnetic behavior.

关 键 词：crystal structure binuclear complex magnetic property DFT calculation 

分 类 号：O641.4[理学—物理化学] O431.2[理学—化学]