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

使用新型不对称桥连配体的金属组件的合理合成和功能化

基本信息

批准号：
11640568
负责人：
OHBA Masaaki
金额：
$ 2.3万
依托单位：
KYUSHU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1999
资助国家：
日本
起止时间：
1999 至 2000
项目状态：
已结题

项目摘要

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

本研究通过具有结构限制因素的新型桥联配体制备了六核环状配体，合成了新型不对称桥联配体3-[1-(2-吡啶)-3，5-二甲基吡唑-4-基]-3，5-戊二酮(HL)。该配体具有两个不同的金属结合部位(‘acac’和‘pypz’)，由于四个甲基的空间位阻，它们被迫相互垂直，结合角度是非线性的，形成约120°的角度。HL与Cux_2·nH_2O(X=ClO_4^-，BF_4^-)以1：1的摩尔比反应得到了铜(II)的配位化合物{[Cu(L)(H_2O)]X·nH_2O}_6。这些配合物具有基本相同的结构，其中铜(II)呈方形锥形构型，N_2O_2赤道平面由一个配体的‘acac’位和另一个配体的‘pypz’位和轴位的配位水形成。六核环状结构是由具有di…空腔的不对称单元的六次重复构成的更长的17.2Å。在整体上，一维沟道结构是由六角单元堆积而成。反阴离子和晶格水分子位于六核单元之间，形成两种相的交替排列。然而，由于它们的相结构，它们的堆积结构对于脱水处理来说是如此脆弱。虽然X射线衍射仪测试结果表明，脱水后催化剂的堆积结构发生了水化，六方环状结构仍保持不变，但对气体的吸附能力并不明显。为了强化通道结构，提高气体吸附能力，合成了三甲氧基苯加合物{[Cu(L)(H2O)]ClO4·4H2O·1/3TMB}6。该化合物保持了原有的一维沟道结构，晶格参数基本相似。TMB分子位于三螺杆轴上，填补了六核环状单元之间的空隙，PXRD结果表明TMB分子对脱水处理具有稳定性，这表明TMB分子作为柱子支撑了堆积结构。TMB加合物的气体吸附能力的评估目前正在进行中。较少