草酰二胺桥联的双核钴（Ⅱ）、镍（Ⅱ）和铜（Ⅱ）配合物的合成与磁性

Synthesis and Magnetism of Binuclear Cobalt(Ⅱ)、Nickel(Ⅱ) and Copper(Ⅱ)Complexes bridged by Oxamidate

已合成四种新的草酰二胺桥联的双核钴（Ⅱ）、镍（Ⅱ）和铜（Ⅱ）配合物：Ｃｏ＿２（ｂｐｙ）＿２（ｏｘｄ）（ＣｌＯ＿４）＿２（１），ＣＯ＿２（Ｍｅ＿２－ｂｐｙ）＿２（ｏｘｄ）（ＣｌＯ＿４）＿２·Ｈ＿２Ｏ（２），Ｎｉ＿２（ｂｐｙ）＿２（ｏｘｄ）（ＣｌＯ＿４）＿２·Ｈ＿２Ｏ（３），Ｃｕ＿２（Ｍｅ）＿２－ｂＰｙ）＿２（ｏｘｄ）（ＮＯ＿３）＿２（４），ｂＰｙ表示２，２＇－联吡啶，Ｍｅ＿２－ｂｐｙ表示４，４＇－二甲基联吡啶，ｏｘｄ表示草酰二胺阴离子。经元素分析、ＩＲ、电子光谱、ＥＳＲ、磁化率及变温磁化率的测定，对上述各配合物进行了表征。配合物（１）和（３）的变温磁化率已测定，其数值用最小二乘法和从自旋哈密顿算符导出的磁方程拟合，求得交换积分Ｊ为－１．４８ｃｍ￣（－１）和－１．８２ｃｍ￣（－１），表明配合物中钴（Ⅱ）－钴（Ⅱ）离子及镍（Ⅱ）－镍（Ⅱ）离子之间仅有极弱的反铁磁自旋交换作用。

Four binuclear Cobalt (Ⅱ)、Nickel (Ⅱ) and Copper(Ⅱ) complexes bridged byoxamidate groups Co_2(bpy)_2(oxd)(ClO_4)_2(1), Co_2(Me_2-bpy)_2(oxd)(ClO_4)_2 ·H_2O_2), Ni_2(bpy)_2(oxd)(ClO_4)_2·H_2O(3),Cu,(Me,- bpy),(oxd)(NO,),(4). (bpy = 2,2'-- bpyridyl, Me -- bpy = 4,4'--bimethylbipyridyl, oxd ￣oxamidate) have been synthesized. All complexes have' beencharacterized by elemental analyses, IR, electronic spectra, ESR, susceptibility andvariabale temperature magnatic susceptibility. The variabale -- temperature magnaticsusceptibility of complexes (1) and (3) (4 -- 300K) heve been determined, and date wereleast squares fit to susceptibility equation derived from the spin Hamitonnian oparatorH = -- ZJS,S,. The exchange integral J is found to be -- 1 .48cmwil and -- 1 .82cm-- 1,indicatingthat an extremely weak antiferromagnetic spin exchange interaction between Co (Ⅱ) -- Co(Ⅱ). fi(Ⅱ) -- Ni(Ⅱ)ions.