具有π…π作用的三维Cu(Ⅰ)配位聚合物的合成结构表征和荧光性质（英文）

Syntheses, Structural Characterization and Fluorescent Properties of 3D Copper(Ⅰ) Coordination Polymers with Extended π…π Interactions

合成了2个铜(Ⅰ)的配位聚合物{[Cu_4(4-bpo)_4(CH_3CN)_4](BF_4)_4}_n(1)和{[Cu_3(4-bpo)_2(4,4′-bipy)(CH_3CN)_6](BF_4)_3}_n(2)(4,4′-bipy=4,4′-bipyridine,4-bpo=2,5-bis(4-pyridyl)-1,3,4-oxadiazole),并对其进行了红外、氢谱、氟谱、硼谱等相关表征,利用X射线单晶衍射仪测定了聚合物的结构。晶体结构研究表明,配位聚合物1通过2,5-二(4-吡啶基)-1,3,4-噁二唑桥连配位作用构筑‘8’形状的结构单元,形成了三维网络结构。引入4,4′-联吡啶配体,导致配合物的结构发生改变:在配合物2中,一维螺旋链通过π…π氢键相互作用组装成不同二维和三维网络结构,说明引入第二配体对改变配合物的超分子结构起关键作用。此外,还研究了配合物1的固态发光性能,显示其存在ILCT电荷跃迁。

Two copper（Ⅰ） coordination polymers, {[Cu4（4-bpo）4（CH3CN）4]（BF4）4}n （1） and {[Cu3（4-bpo）2（4,4＇-bipy） （CH3CN）6]（BF4）3}n （2） （4,4＇-bipy=4,4＇-bipyridine, 4-bpo=2,5-bis（4-pyridyl）-l,3,4-oxadiazole）, have been synthesized and characterized by IR, ^1H NMR, ^19F NMR, ^11B NMR and X-ray crystal structure analysis. Structural analysis shows that complex 1 contains repeat ＂8＂-shape building units that are linked to each other by the bridging coordination action of 4-bpo, forming a 3D network. The introduction of 4,4＇-bipyridine results in the size variance of complex 2, which consists of 1D meso-helical chain, 2D muhilayer architecture and 3D network formed by intermoleeular π…π interactions and hydrogen bonds. All these indicate that the change of secondary ligand might be the key of the extended supramolecular networks of the lower-dimensional coordination polymers. Moreover, solid-state emission spectrum of complex 1 displays the existence of ILCT excited states. CCDC： 1043969, 1; 1043970, 2.