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首页> 外文期刊>RSC Advances >Unusual solvent-mediated hydrolysis of dicarboxylate monoester ligands in copper(II) complexes toward simultaneous crystallization of new dicarboxylate derivatives
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Unusual solvent-mediated hydrolysis of dicarboxylate monoester ligands in copper(II) complexes toward simultaneous crystallization of new dicarboxylate derivatives

机译：溶剂介导的铜（II）配合物中二羧酸单酯配体的异常水解，同时使新的二羧酸衍生物结晶

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摘要

A series of copper(II) complexes, [Cu(cmb)(2)(im)(2)] (1), [Cu(cmn)(2)(im)(4)] (3) and [Cu(cmp)(2)(im)(2)] (5), bearing various dicarboxylate monoester derivatives, [cmb = 2-carbomethoxy-benzoate; cmn = 8-carbomethoxy-naphthalene-1-carboxylate; cmp = 2-carbomethoxy-phenyl-2-benzoate], were generated from copper(II) acetate, imidazole (im) and an aromatic anhydride [phthalic, 1,8-naphthalic or biphenic anhydride for 1, 3 or 5, respectively]. Unusual solvent-mediated transformations of the crystals of two copper dicarboxylate monoester complexes to new crystals of the corresponding dicarboxylate derivatives by the hydrolysis of ester groups were observed and investigated. Crystals of 1 underwent a transformation to crystals of copper(II) phthalate 2D coordination polymer {[Cu-2(pht)(2)(im)(4)center dot H2O]center dot H2O}(n) (2) (pht = phthalate) upon moistening with aqueous methanol. Similarly, crystals of 3, after wetting with aqueous dimethylformamide (DMF), were transformed to crystals of a metallacycle [Cu(nap)(im)(DMF)(H2O)](2) (4) (nap = 1,8-naphthalenedicarboxylate). In contrast to 1 and 3, the crystals of 5 were found to be stable under ambient conditions. Compounds 1-5 were characterized by IR and UV-vis spectroscopy and single crystal and powder X-ray diffraction. Topological analysis showed that in the 1 -> 2 transformation the overall 2D network topology was modified from the 4-connected H-bonded sql net [Shubnikov tetragonal plane net] to the 3-connected metal-organic hcb net [Shubnikov hexagonal plane net/(6, 3)], whereas no topology change was detected during an analogous 3 -> 4 transformation, with both structures exhibiting topologically equal H-bonded sql nets.
机译：一系列铜（II）配合物[Cu（cmb）（2）（im）（2）]（1），[Cu（cmn）（2）（im）（4）]（3）和[Cu（ cmp）（2）（im）（2）]（5），带有各种二羧酸单酯衍生物，[cmb = 2-碳甲氧基-苯甲酸酯; cmn = 8-碳甲氧基-萘-1-甲酸;由乙酸铜（II），咪唑（im）和芳族酸酐[分别为1、3或5的邻苯二甲酸，1,8-萘或联苯酸酐]生成cmp = 2-碳甲氧基-苯基-2-苯甲酸酯] 。观察和研究了通过酯基的水解，溶剂介导的两个二羧酸铜单酯铜配合物晶体向相应的二羧酸衍生物的新晶体的不寻常转化。 1的晶体转变为邻苯二甲酸铜（II）二维配位聚合物{[Cu-2（pht）（2）（im）（4）中心点H2O]中心点H2O}（n）（2）（pht =邻苯二甲酸酯），然后用甲醇水溶液润湿。同样，用二甲基甲酰胺水溶液（DMF）润湿后的3晶体转化为金属环[Cu（nap）（im）（DMF）（H2O）]（2）（4）（nap = 1,8-萘二甲酸）。与1和3相反，发现5的晶体在环境条件下是稳定的。通过IR和UV-可见光谱以及单晶和粉末X射线衍射表征化合物1-5。拓扑分析显示，在1-> 2转换中，整个2D网络拓扑从4连接的H键合sql网络[Shubnikov四边形平面网]修改为3连接的金属有机hcb网络[Shubnikov六角形平面网/ （6，3）]，而在类似的3-> 4转换过程中未检测到拓扑变化，两个结构均显示拓扑相等的H键合sql网络。

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