具有不同类型桥基的双核Cu(Ⅱ)-Schiff碱配合物的合成和晶体结构

Preparation, Structure and Properties of Dinuclear Cu(Ⅱ) Schiff Base Complexes with Different Type of Bridging Groups

合成了３个分别以Ｃ２Ｏ２－４（［Ｃｕ２（Ｌ１）２（ｏｘ）］，１），ＡｃＯ－（［Ｃｕ２（ＡｃＯ）（Ｌ２）２］ＢＦ４，２）和酚氧（［Ｃｕ２（Ｌ３）２］（ＣｌＯ４）２，３）为桥基的双核铜配合物，并测定了１的复配合物［Ｃｕ２（Ｌ１）２（ｏｘ）］·［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ（１′）及２和３的晶体结构．Ｘ射线衍射结果表明：１′，２和３分别属于Ｆｄｄｄ，Ｐ２１／ｃ和Ｐ２１／ｃ空间群．晶胞参数：［Ｃｕ２（Ｌ１）２（ｏｘ）］［Ｆｅ（ＯＨ）２（Ｈ２Ｏ）４］ＣｌＯ４·Ｈ２Ｏ，ａ＝２．４３９０（４）ｎｍ，ｂ＝３．０５３８（６）ｎｍ，ｃ＝１．８４９４（６）ｎｍ，α＝β＝γ＝９０．００°；２，ａ＝０．８４７（１）ｎｍ，ｂ＝２．６５４２（８）ｎｍ，ｃ＝１．４１００（６）ｎｍ，β＝９１．３４（６）°；３，ａ＝０．７６４６（３）ｎｍ，ｂ＝１．６９８３（３）ｎｍ，ｃ＝２．４４１７（３）ｎｍ，β＝９７．

Three dinuclear Cu(Ⅱ) complexes with oxalate ( Cu 2(L1) 2(ox) , 1), acetate ( Cu 2(AcO)(L2) 2 BF 4 , 2) and phenolate group( Cu 2(L3) 2 (ClO 4) 2, 3)as bridging group, individually, were synthesised, and the crystal structures of composite complex Cu 2(L1) 2(ox) \5 Fe(OH) 2(H 2O) 4 ClO 4\5H 2O (1′) and complexes 2 and 3 were determined. X ray crystal structure analyses comfirm that the crystals of 1′, 2 and 3 exist in Fddd , P 2 1/ c and P 2 1/ c space group, respectively. The crystal cell parameters of 1′ are: a =2 439 0(4) nm, b = 3 053 8(6) nm , c =1 849 4(6) nm, α=β=γ =90.00° and these of 2 are: a =0.847(1) nm, b =2 654 2(8) nm, c =1 410 0(6) nm, β =91.34(6)°; 3: a =0.764 6(3) nm, b =1.698 3(3) nm, c =2.441 7(3) nm, β =97.11°. Electrochemical investigations of 1 and 3 [STBZ]show that bicopper(Ⅱ) centre experiences a mix valence species during the course of reduction scan.