Rational synthesis and functionalization of metal assemblies using a new unsymmetric bridging ligand

在这项研究中，六核环组装是由结构限制的一种新的桥接配体和具有结构限制因素的;一种新的非对称性桥接配体3-[1-（2-吡咯烷基）-3，5-二甲基吡唑-4-基]-3，5-五甲苯-二酮（HL）是预先准备的。这个配体有两个不同的金属绑定网站（“acac”和“pipz”网站），它们被强迫对四个甲基组的其他顺序进行静态的暗示，以及绑定角度是非线性的，形成了一个加利福尼亚的角度。120度。1 ： 1 molar ratio has given copper （II） assemblies {[Cu （L）（H_2O）] X·nH_2O}_6.这些复杂性在Cu （II）结构中采用一个N_2O_2等平面形成的“acac”站点和另一个“pipz”站点和轴站点的另一个“pypz”站点和一个“坐标水”站点的N_2O_2等平面。而六核环结构是由六次重复的不对称单元形成的，它具有一个洞穴。 ... More ameter of 17.2弧度。在大块中，一维信道结构是由六角单元组成的。反阴离子和晶格水分子在六核单元之间被定位，形成了两种相位的替代安排。However，他们的包装结构对相位结构来说是如此脆弱，因为脱水治疗是如此的脆弱。还显示了通过氢化和六环结构重新构建的包装安排即使在脱水后也得到了维护，这些复杂性的气体吸收能力也不那么明显。重新增加通道结构，提高气体吸收能力，三甲氧基苯（TMB）添加， {[Cu （L）（H_2O）] ClO_4·4H_2O·1/3 TMB}_6准备好了。这个复合物维护了原始的1-D通道结构，与大多数相似的晶格参数。TMB分子被定位在三个螺杆轴上，并填充了六核循环单元之间的间隙PXRD结果显示了对脱水处理的稳定性，哪些建议将TMB分子作为支柱将包装结构作为可持续的材料？对TMB补充剂气体吸收能力的估计目前正在进行中。Less（低）

In this research, hexanuclear cyclic assemblies have been prepared by a new bridging ligand having factors of structural restriction.A new unsymmetric bridging ligand 3-[1-(2-pyridyl)-3, 5-dimethylpyrazole-4-yl]-3, 5-pentane-dione (HL) was prepared. This ligand has two dissimilar metal-binding sites ('acac' and 'pypz' sites) which are forced to be perpendicular to each other due to steric hindrance of four methyl groups and the binding angle is nonlinear to form an angle of ca. 120°. Reaction of HL and CuX_2・nH_2O (X= ClO_4^-, BF_4^-) in the 1 : 1 molar ratio has given copper (II) assemblies {[Cu (L)(H_2O)] X・nH_2O}_6. These complexes have essentially same structure where the Cu (II) adopts a square-pyramidal geometry with a N_2O_2 equatorial plane formed by the 'acac' site of one ligand and the 'pypz' site of another ligand and coordination water at the axial site. And the hexanuclear cyclic structure was constructed by the six times repeat of the asymmetric unit having a cavity of di … More ameter of 17.2 Å. In the bulk, 1-D channel structure was formed by stacking of the hexagonal units. Counter anion and lattice water molecules were located between hexanuclear units, which formed an alternate arrangement of two kinds of phases. However, their packing structure was so fragile against a dehydration treatment owing to the phase structure. Although PXRD results showed that the packing arrangement was reconstructed by hydration and the hexagonal cyclic structure was maintained even after dehydration, gas adsorption ability of these complexes was not so remarkable.In order to reinforce the channel structure and to improve the gas adsorption ability, trimethoxybenzene (TMB) adduct, {[Cu (L)(H_2O)] ClO_4・4H_2O・1/3TMB}_6 was prepared. This compound maintained the original 1-D channel structure with mostly similar lattice parameters. TMB molecules were located on three-screw axis and filled the gap between hexanuclear cyclic units PXRD results showed stability against dehydration treatment, which suggests that TMB molecules sustained the packing structure as pillars. The estimation of gas adsorption ability of the TMB adduct is now in progress. Less