Hari Nairita, Mandal Shuvankar, Jana Arpita, Sparkes Hazel A, Mohanta Sasankasekhar
Department of Chemistry, University of Calcutta 92 A. P. C. Road Kolkata 700 009 India
School of Chemistry, University of Bristol Cantock's Close Bristol BS8 1TS UK.
RSC Adv. 2018 Feb 14;8(14):7315-7329. doi: 10.1039/c7ra13763j.
Six trinuclear CuMCu compounds (M = Cu, Ni, Co, Fe, Mn, Zn) derived from the Schiff base ligand, HL (2 + 1 condensation product of salicylaldehyde and -1,2-diaminocyclohexane) are reported in this investigation. The composition of the metal complexes are [{CuL(ClO)}Cu(HO)]·2HO (1), [{CuL(ClO)}{Ni(HO)}{CuL}]ClO·CHCOCH (2), [{CuL(ClO)}{Co(CHCOCH)(HO)}{CuL(CHCOCH)}]ClO (3) and isomorphic [{CuL(ClO)}M(CHOH)] (4, M = Fe; 5, M = Mn; 6, M = Zn). Two copper(ii) ions in 1-6 occupy NO compartments of two L ligands, while the second metal ion occupies the O(phenoxo) site provided by the two ligands, , the two metal ions in both CuM pairs are diphenoxo-bridged. Positive ESI-MS of 1-6 reveals some interesting features. Variable-temperature and variable-field magnetic studies reveal moderate or weak antiferromagnetic interactions in 1-6 with the following values of magnetic exchange integrals ( = -2 type): = -136.50 cm and = 0.00 for the CuCuCu compound 1; = -22.16 cm and = -1.97 cm for the CuNiCu compound 2; = -14.78 cm and = -1.86 cm for the CuCoCu compound 3; = -6.35 cm and = -1.17 cm for the CuFeCu compound 4; = -6.02 cm and = -1.70 cm for the CuMnCu compound 5; = -2.25 cm for the CuZnCu compound 6 ( is between two Cu in the NO compartments; is between Cu and M through a diphenoxo bridge).
本研究报道了六种由席夫碱配体HL（水杨醛与1,2 - 二氨基环己烷的2 + 1缩合产物）衍生的三核CuMCu化合物（M = Cu、Ni、Co、Fe、Mn、Zn）。金属配合物的组成分别为[{CuL(ClO)}Cu(HO)]·2HO（1）、[{CuL(ClO)}{Ni(HO)}{CuL}]ClO·CHCOCH（2）、[{CuL(ClO)}{Co(CHCOCH)(HO)}{CuL(CHCOCH)}]ClO（3）以及同构的[{CuL(ClO)}M(CHOH)]（4，M = Fe；5，M = Mn；6，M = Zn）。1 - 6中的两个铜（II）离子占据两个L配体的NO配位位点，而第二个金属离子占据两个配体提供的O（苯氧）位点，即CuM对中的两个金属离子通过双苯氧桥相连。1 - 6的正电喷雾电离质谱（ESI - MS）显示出一些有趣的特征。变温和变场磁性研究表明1 - 6中存在中等或弱的反铁磁相互作用，其磁交换积分值如下（ = -2 类型）：对于CuCuCu化合物1， = -136.50 cm且 = 0.00；对于CuNiCu化合物2， = -22.16 cm且 = -1.97 cm；对于CuCoCu化合物3， = -14.78 cm且 = -1.86 cm；对于CuFeCu化合物4， = -6.35 cm且 = -1.17 cm；对于CuMnCu化合物5， = -6.02 cm且 = -1.70 cm；对于CuZnCu化合物6， = -2.25 cm（ 在NO配位位点的两个Cu之间； 通过双苯氧桥在Cu和M之间）。
