Cu(II)-Silsesquioxanes as Secondary Building Units for Construction of Coordination Polymers: A Case Study of Cesium-Containing Compounds

Korlyukov Alexander A.; Vologzhanina Anna V.; Buzin Mikhail I.; Sergienko Nataliya V.; Zavin Boris G.; Muzafarov Aziz M.

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Cu(II)-Silsesquioxanes as Secondary Building Units for Construction of Coordination Polymers: A Case Study of Cesium-Containing Compounds

机译：铜（II）-倍半硅氧烷作为配位聚合物构建的二级构件：含铯化合物的案例研究

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Five new bi- and trimetallic copper-organosilsesquioxanes {[VinSiO(2)](12)Cu4Cs4(BuOH)(2)(EtOH)(2)(MeOH)}center dot 2BuOH (1), {[PhSiO2](12)CU4CS2K2(1,4-dioxane)(9)-(H2O)(2)}center dot 3.4(1,4-dioxane) (2), {[PhSiO2](12)Cu4Cs4(DMF)(6)}center dot 2DMF (3), {[MeSiO2](12)Cu4Cs4(THF)(4.5)(MeOH)(2)(H2O)(0.25)} (4), and {[MeSiO2](24)Cu10Cs6(OH)(2)(THF)(4.2)(MeOH)(4.1)-(H2O)(0.7)} (5) have been synthesized by an exchange reaction between discrete cage alkali,copper-siloxane and cesium chloride (1, 2) or cesium carbonate (4, 5) or by interaction of copper-phenylsiloxane with cesium phenylsiloxanolate (3). While in 1-4 the alkali,copper-silsesquioxane cage remains stable during reaction procedures, complex 5 was obtained by unexpected dimerization of two cages. The neutral cages act with solvent molecules and neighboring cages as square (1, 3, 5), tetrahedral (4), or octahedral (2) nodes giving, respectively, the two periodic (2D) sql net, and the three-periodic (3D) dia or pcu nets. The roles of the cage structure, nature of metal atoms, and organic coating in the formation of one-, two-, and three-periodic coordination polymers are discussed in the example of newly synthesized and previously obtained alkali,copper-organosiloxanes and copper-organosiloxanes with sandwich or globular cage structures. What's more, the charge distribution in crystals of 1-3 was analyzed by means of Bader's Quantum Theory of Atoms in-Molecules approach giving evidence of relatively strong bonding between neighboring cages.

机译：五个新的双金属和三金属铜有机倍半硅氧烷{[VinSiO（2）]（12）Cu4Cs4（BuOH）（2）（EtOH）（2）（MeOH）}中心点2BuOH（1），{[PhSiO2]（12） CU4CS2K2（1,4-二恶烷）（9）-（H2O）（2）}中心点3.4（1,4-二恶烷）（2），{[PhSiO2]（12）Cu4Cs4（DMF）（6）}中心点2DMF（3），{[MeSiO2]（12）Cu4Cs4（THF）（4.5）（MeOH）（2）（H2O）（0.25）}（4）和{[MeSiO2]（24）Cu10Cs6（OH）（2））（THF）（4.2）（MeOH）（4.1）-（H2O）（0.7）}（5）是通过分散的笼状碱，铜-硅氧烷与氯化铯（1、2）或碳酸铯之间的交换反应合成的（4、5）或通过铜-苯基硅氧烷与苯基硅氧烷氧硅烷化铯（3）的相互作用。在1-4中，碱，铜-倍半硅氧烷笼在反应过程中保持稳定，而复合物5是通过两个笼的意外二聚得到的。中性笼与溶剂分子一起作用，相邻笼作为方形（1、3、5），四面体（4）或八面体（2）节点，分别给出两个周期性（2D）sql网和三个周期性（ 3D）dia或pcu网。在新合成并预先获得的碱金属，铜-有机硅氧烷和铜-铜的例子中，讨论了笼型结构，金属原子的性质以及有机涂层在形成一，二和三周期配位聚合物中的作用。具有三明治或球形笼状结构的有机硅氧烷。此外，借助巴德量子原子分子论方法分析了1-3晶体中的电荷分布，从而证明了相邻笼之间的结合力相对较强。

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《Crystal growth & design》 |2016年第4期|共10页
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Korlyukov Alexander A.; Vologzhanina Anna V.; Buzin Mikhail I.; Sergienko Nataliya V.; Zavin Boris G.; Muzafarov Aziz M.;
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机译：铜（II）-倍半硅氧烷作为配位聚合物构建的二级构件：含铯化合物的案例研究
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Cu(II)-Silsesquioxanes as Secondary Building Units for Construction of Coordination Polymers: A Case Study of Cesium-Containing Compounds

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