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首页> 外文期刊>Crystal growth & design >Homonuclear and Heteronuclear Complexes of Calix[4]-bismonothiacrown?5 with Oligomer and Polymer Structures
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Homonuclear and Heteronuclear Complexes of Calix[4]-bismonothiacrown?5 with Oligomer and Polymer Structures

机译：Calix [4] -bismonothiacrown？5具有低聚物和聚合物结构的同核和异核配合物

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摘要

Homo- and heteronuclear complexes (1?7) of calix[4]-bismonothiacrown-5 (L) with mercury(II), cadmium(II), copper(I), and potassium(I) salts adopting dimer, tetramer, one-dimensional (1D), and two-dimensional (2D) polymer structures with different coordination modes and connectivity patterns were prepared and structurally characterized. Reactions of L with mercury(II) iodide and mercury(II) thiocyanate afforded a dimer complex [Hg_4(L)_2I_8]·CH_2Cl_2 (1) and a 1D coordination polymer {[Hg_2(L)(SCN)_4]·CH_2Cl_2}n (2), respectively, in which the exocyclic dimercury(II) complex units of L are doubly linked by the anions. Reactions of L with cadmium(II) iodide in the absence and the presence of mercury(II) iodide gave isostructural 1D coordination polymers [Cd2(L)I4]n (3) and {[Cd_2(L)I_4][CdHg(L)I_4]}_n (4), respectively. In the isostructure of 3 and 4, the ligands are alternately linked by the exocyclic M-I2-M squares via monocadmium(II)-mediated and dicadmium(II)-mediated modes, respectively. Reaction of L with copper(II) thiocyanate in the presence of potassium(I) thiocyanate afforded a discrete complex {[(K_2L)_4Cu_6(SCN)_(10)][K_2L]_2[Cu(SCN)_3]_3·2CH_2Cl_2· CH_3CN} (5) consisting of three separated parts: dipotassium(I) tetramer part linked with a oligomer copper(I) thiocyanate backbone, dipotassium(I) monomer part, and trithiocyanato copper(I) complex part. When a mixture of mercury(II) thiocyanate and potassium(I) thiocyanate was used, a grid-type 2D heteronuclear polymer complex [Hg_3(K_2L)(SCN)_8]_n (6) in which the 1D mercury(II) thiocyanato backbones cross-linked by endocyclic dipotassium(I) complex units of L was isolated. One pot reaction of L with a mixture of iodide salts of potassium(I), mercury(II), and cadmium(II) gave a binary mixed product of a discrete complex [(K_2L)_2(Cd_3I_8)][Cd_4I_(10)] (7) and a heteronuclear 2D network (8) which can be manually separated because of the colorless platy and orange?yellow block shapes of the crystals, respectively. In 7, the endocyclic dipotassium(I) complex of L is linked by Cd_3I_8 clusters.
机译：杯[4] -bismonothiacrown-5（L）与汞（II），镉（II），铜（I）和钾（I）盐的同核和异核配合物（1？7），采用二聚体，四聚体，一种制备了具有不同配位模式和连接方式的三维（1D）和二维（2D）聚合物结构，并进行了结构表征。 L与碘化汞（II）和硫氰酸汞（II）的反应得到二聚体[Hg_4（L）_2I_8]·CH_2Cl_2（1）和一维配位聚合物{[Hg_2（L）（SCN）_4]·CH_2Cl_2} n（2），其中L的环外二聚汞（II）复杂单元被阴离子双重连接。在不存在和存在碘化汞的条件下，L与碘化镉（II）的反应得到同构一维配位聚合物[Cd2（L）I4] n（3）和{[Cd_2（L）I_4] [CdHg（L） ）I_4]} _ n（4）。在3和4的同构结构中，配体分别通过单镉（II）介导的模式和双镉（II）介导的模式由环外M-I2-M正方形交替连接。在硫氰酸钾（I）的存在下，L与硫氰酸铜（II）的反应得到了离散的络合物{[（（K_2L）_4Cu_6（SCN）_（10）] [K_2L] _2 [Cu（SCN）_3] _3·2CH_2Cl_2 ·CH_3CN}（5）由三个分离的部分组成：与低聚硫氰酸铜（I）骨架连接的二钾（I）四聚体部分，二钾（I）单体部分和三硫氰酸根合铜（I）配合物部分。当使用硫氰酸汞（II）和硫氰酸钾（I）的混合物时，其中一维汞（II）硫氰酸根骨架的网格型2D杂核聚合物配合物[Hg_3（K_2L）（SCN）_8] _n（6） L的内环双钾（I）复杂单元交联的分离。 L与钾（I），汞（II）和镉（II）的碘盐混合物进行一锅反应，得到离散复合物[（K_2L）_2（Cd_3I_8）] [Cd_4I_（10）的二元混合产物]（7）和可以手动分离的异核2D网络（8），分别是由于晶体的无色板状和橙黄色块状。在7中，L的内环双钾（I）络合物由Cd_3I_8簇连接。

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