Binuclear copper(II) complexes with N₃S-coordinate tripodal ligand and mixed azide-carboxylate bridges: Synthesis, crystal structures and magnetic properties

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• 作者：Mehul H. Sadhu^a ; Corine Mathoniere^b ; ^c ; Yogesh P. Patil^d ; Sujit Baran Kumar^a ; ^{kumarsujitbaran@gmail.com}
• 关键词：N3S donor ligand ; Binuclear Cu(II) complexes ; Bridging ligands ; Structure ; Magnetic studies
• 刊名：Polyhedron
• 出版年：2017
• 出版时间：28 January 2017
• 年：2017
• 卷：122
• 期：Complete
• 页码：210-218
• 全文大小：1551 K
• 卷排序：122

文摘

One new N3S-coordinate tetradentate ligand N,N-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine (bdmpe) has been synthesized and characterized. Two double end-on azide bridged copper(II) complexes [Cu(bdmpe)(μ1,1-N3)]2(X)2 [X = ClO4−, PF6−] and two triple bridged copper(II) complexes [Cu2(dmpe)2(μ1,1-N3)2(Y)]PF6 [where dmpe = N-((3,5-dimethyl-1H-pyrazol-1-yl)methyl)-2-(phenylthio)ethan-1-amine, Y = CH3COO− or HCOO−] have been synthesized and characterized. Ligand (dmpe) has been formed from ligand bdmpe during in situ complexation reaction. Crystal structures of the three complexes [Cu(bdmpe)(N3)]2(ClO4)2 (1), [Cu2(dmpe)2(μ1,1-N3)2(CH3COO)]PF6 (3) and [Cu2(dmpe)2(μ1,1-N3)2(HCOO)]PF6 (4) have been solved by single crystal X-ray diffraction studies and the structural data revealed that the complex [Cu2(bdmpe)2(N3)2](ClO4)2 is binuclear and two copper(II) centers are bridged by a pair of (μ1,1) N3− ion whereas the structures of complexes 3 and 4 are binuclear with triple bridged and two adjacent copper(II) centers are bridged by pair of N3− ions with end-on (μ1,1) coordination mode and one acetate/formate group with syn–syn coordination mode, respectively. Variable temperature (4–273 K) magnetic measurement shows that complex 1 has no magnetic interaction whereas complexes 3 and 4 have weak antiferromagnetic interactions with J values −15.3(1) cm−1 for complex 3 and −17.8(1) cm−1 for complex 4.