Crystal Structures, Dielectric, and CO_2-Adsorption Properties of One-Dimensional [Cu(II)_2(Adamantane-1-carboxylate)_4(pyrazine)]_∞ Coordination Polymers with Polar Ligands
Crystal Structures, Dielectric, and CO_2-Adsorption Properties of One-Dimensional [Cu(II)_2(Adamantane-1-carboxylate)_4(pyrazine)]_∞ Coordination Polymers with Polar Ligands
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极性配体一维[Cu(II)_2(金刚烷-1-羧酸酯)_4(吡嗪)]_∞配位聚合物的晶体结构、介电性能和CO_2吸附性能
DOI：
10.1166/sam.2014.1831
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发表时间：
2014
影响因子：
0.9
通讯作者：
and Tomoyuki Akutagawa
中科院分区：
文献类型：
--
作者：
Kiyonori Takahashi;Norihisa Hoshino;Shin-ichiro Noro;Takayoshi Nakamura;and Tomoyuki Akutagawa
合成了双核Cu（II）配位聚合物[Cu（II）（ADCOO）4（pz）]∞（1），[Cu（II）（ADCOO）4（F-pz）]∞（2），[Cu（II）（Cl-ADCOO）4（pz）]∞（3），其中ADCOO，Cl-ADCOO，pz，F-pz分别为金刚烷-1-羧酸酯，3-氯金刚烷-1-羧酸酯，吡嗪，2-氟吡嗪.配体ADCOO和Cl-ADCOO分别与两个Cu（II）离子形成双核配体[Cu（II）（ADCOO）4 ]和[Cu（II）（Cl-ADCOO）4]，再通过轴向双齿配体pz或F-pz连接，形成一维配位聚合物。虽然在晶体1、2和3的典型结构中观察到1D配位聚合物，但是聚合物3的堆积结构不同于晶体1和2的堆积结构。在1和2中观察到三维（3D）交叉聚合物阵列作为具有I-43 d空间群的立方晶体系统，而3的一维聚合物的二维阵列与[Cu（II）（C6 H5 COO）4（pz）]∞晶体相同。2的晶体结构不受极性F基团引入轴向pz配体的影响，而Cl-取代基引入ADCOO配体显着修改的配合物的包装结构。X射线晶体结构分析表明，2中的F-pz和3中的Cl-ADCOO在110 K时是静态的。介电常数的绝对值以3、2和1的顺序减小，这与配体的偶极矩一致。在195 K下，在晶体1、2和3中没有观察到CO2气体吸附-脱附过程。1和2中的3D叉指型聚合物排列以及Cl-ADCOO配体之间的强偶极-偶极相互作用不是CO2气体吸附-脱附中结构变化的原因。
Cu(II) binuclear coordination polymers of [Cu(II)(ADCOO)4(pz)]∞ (1), [Cu(II)(ADCOO)4(F-pz)]∞ (2), and [Cu(II)(Cl-ADCOO)4(pz)]∞ (3) were prepared, where ADCOO, Cl-ADCOO, pz, and F-pz are adamantane-1-carboxylate, 3-chloroadamantane-1-carboxylate, pyrazine, and 2-fluoropyrazine, respectively. The Cu(II) binuclear units of [Cu(II)(ADCOO)4 ] and [Cu(II)(Cl-ADCOO)4] were formed by the four bridging ligands of ADCOO and Cl-ADCOO to the two Cu(II) ions, respectively, which were further connected by the axial bidentate ligands of pz or F-pz, to form one-dimensional (1D) coordination polymers. Although the 1D coordination polymers were observed in the typical structures of crystals 1, 2, and 3, the packing structure of polymer 3 was different from those of crystals 1 and 2. Three-dimensional (3D) interdigitated polymer arrays were observed in 1 and 2 as cubic crystal systems with the I-43d space group, whereas the two-dimensional array of 1D polymers of 3 was the same as that of the [Cu(II)(C6H5COO)4(pz)]∞ crystal. The crystal structure of 2 was not affected by the introduction of a polar F group into the axial pz ligand, whereas the introduction of the Cl-substituent into the ADCOO ligand significantly modified the packing structure of the coordination polymers. The polar ligands of F-pz in 2 and Cl-ADCOO in 3 were static at 110 K according to X-ray crystal structural analyses. The absolute magnitude of the dielectric constants was decreased in the order of 3, 2, and 1, which is consistent with the dipole moments of the ligands. No CO2 gas adsorption–desorption processes were observed in crystals 1, 2, and 3 at 195 K. The 3D interdigitated polymer arrangements in 1 and 2, and the strong dipole–dipole interaction between Cl-ADCOO ligands, were not responsible for the structural changes in the CO2 gas adsorption–desorption.