摘要
设计和合成有机氢键超分子和配位氢键超分子是超分子化学的重要分支。有机氢键超分子是通过分子间的氢键、π-π堆积等非共价键作用形成的聚集体。配位氢键超分子则是通过对金属离子和配体的选择可以理性地设计和合成具有特定结构单元及特殊功能的配合物。
本研究合成了两个双齿甜菜碱衍生物1,5-二(3-羧基吡啶基)-N-甲基二乙胺( L1)和1,5-二(4?羧基吡啶基)?N?甲基二乙胺(L2 ),并对L1的高氯酸盐进行了结构表征。用这两种配体与Zn(II)、Cd(II)和Ag(I)的不同的金属盐反应,得到了八个配合物,研究了配体对不同金属盐的配位能力及构筑配合物三维网络结构的能力。这八个配合物分别是: {[ZnL1Cl_2 ]·1.5H_2O}_n(2)、{ [ZnL1_2 ]·2ClO_4·H_2O}n(3)、{ [ZnL1(SCN) 2 ]·H_2O}n(4)、{[CdL1Cl_2 ]·H_2O}_n(5)、{[CdL1_2 ]·2ClO_4·H_2O}n(6)、[ZnL2Cl_2·H_2 O]n(7)、{[Zn_2 L2_4 (H_2O)_6 ]·4ClO_4·H_2O·DMF}n(8)和{[Ag_3 L2_2 (H_2O)]·3PF_6·4H_2 O}n(9),对所有的配合物用红外光谱和单晶X?射线衍射结构分析方法进行了表征。
结构分析表明:(1)在配合物中,配体L1和L2中的羧基采用了三种配位模式:在与Zn(II)盐反应生成的配合物{[ZnL1Cl 2 ] ? 1.5H 2 O}n、{[ZnL1_2 ]·2ClO_4·H_2 O}_n、{[ZnL1(SCN) 2 ]·H_2O}n、[ZnL2Cl_2·H_2 O]n和{[Zn_2L2_4 (H_2O)_6 ]·4ClO_4·H_2O·DMF}_n中全部采用单齿模式;在与Cd(II)盐反应生成的配合物{[CdL1Cl_2 ]·H_2O}n中采用双齿螯合配位,而在配合物{[CdL1_2 ]·2ClO_4·H_2O}n中同时出现了单齿和双齿螯合两种配位模式;在配合物{[Ag_3 L2_2 (H_2 O)]·3PF6·4H_2O}n中是以双齿桥联的方式参与配位的。(2)配合物{[ZnL1Cl_2]·1.5H_2O}n和{[CdL1Cl_2 ]·H_2O}n是由L1分别和ZnCl_2、CdCl_2反应得到的,但是由于金属离子的不同,使得配体采用不同配位模式。(3)配合物{[ZnL1Cl·2]·1.5H_2O}n和{[ZnL1_2 ]·2ClO_4·H_2O}n是由L1分别和ZnCl_2、Z n(ClO_4 )2反应得到的,但是由于阴离子的不同,对中心原子的配位环境产生了重要影响;在配合物{[Zn_2 L2_4 (H_2O)_6 ]·4ClO_4·H_2 O·DMF}n和[ZnL2Cl 2 ? H 2 O]n中也存在相似的规律。(4)氢键在网络构筑中发挥了重要作用, [HL_2 ClO 4]n、[ZnL2Cl 2 ? H 2 O]n和{[Zn 2 L2 4 (H 2 O) 6 ] ? 4ClO4 ? H 2 O ? DMF}n中一维结构的构筑都依赖于氢键。(5)配合物{[Ag_3 L2_2 (H_2 O)]·3PF6·4H_2 O}n中,Ag(I)中心原子被配体桥联形成了一维的Ag(I)原子簇结构;在该化合物中,一维的配位链通过与PF6-阴离子的C ? H L F弱氢键作用而扩展为三维隧道结构。
Design and synthesis of organic hydrogen-bonded and coordination hydrogen- bonded supramolecules are an important field in supramolecular chemistry. Organic hydrogen-bonded supramolecules is formed by non-bonding interactions, such as hydrogen bonds,π-πstacking etc. between molecules, while coordination hydrogen-bonded supramolecules of special structure and special functions can be reasonably designed and synthesized by properly choosing metal ions and ligands.
In present studies, two novel double betaine ligands, namely 1,5·bis(3-carboxy- pyridinium)-N-methyl-diethylamine (L1) and 1,5-bis(4-carboxy-pyridinium)-N– methyl-diethylamine ( L2 ) have been synthesized and allowed to interact with various metal salts of Zn(II),Cd(II) and Ag(I) to investigate their coordination behavior and the ability of constructing coordination supramolecules. The single crystals of eight coordination compounds with the former two ligands, namely L1 and L2 , were obtained, and their molecular and crystal structures have been determined by X-ray single crystal structure analysis. The compounds include: {[ZnL1Cl_2 ]·1.5H_2 O}n(2), {[ZnL1_2 ]·2ClO_4·H_2 O}_n(3), {[ZnL1(SCN) 2 ]·H 2 O}n(4),{[CdL1Cl_2 ]·H_2 O}n(5), {[CdL1_2 ]·2ClO 4·H_2O}n(6), [ZnL_2Cl_2·H 2 O]n(7),{[Zn_2 L2_4 (H_2 O)_6 ]·4ClO_4·H_ 2 O·DMF}n(8) and {[Ag 3 L2_2 (H_2 O)]·3PF6·4H 2 O}n(9).
The results show that: (1) The carboxylate group involved in ligand of L adopted three coordination fashions. Monodentate mode has been acted in compounds {[ZnL1Cl_2 ]·1.5H_2 O}n, {[ZnL1_2 ]·2ClO_4·H_2O}n, {[ZnL1(SCN) 2 ]·H_ 2 O}n,[ZnL2Cl_2·H_2 O]n and {[Zn_2 L2_4 (H_2 O)_6 ]·4ClO_4·H_2O·DMF}n, while chelate coord ination mode has been adopted in compounds {[CdL1Cl 2 ]·H 2 O}n. In compound {[CdL1_2 ]·2ClO_4·H_2O}n, one of carboxylate group of L1 acts in monodentate mode and the other in chelate coordination mode. However, syn-syn bridging mode was adopted in compound {[Ag_3 L2_2 (H 2 O)]·3PF6·4H 2 O}n. (2) Metal ion with different coordination geometry and different metal atom radius will affect the formation of network. In compound {[ZnL1Cl_2 ]·1.5H_2 O}nand {[CdL1Cl_2 ]·H_2 O}n, the carboxylate group adopted different coordination mode due to different coordination geometry and different metal atom radius. (3) In coordination polymers {[ZnL1Cl_2 ]·1.5H_2O}n and derived from the ligand L1, the cations are Zn(II) , but the anions are Cl - and ClO4·, respectively; The same law is exhibited in [ZnL2Cl_2·H_2 O]n and {[Zn_2 L2_4 (H_2O) 6 ]·4ClO_4·H_2O·DMF}n.
The nature of anions has great influence on the configuration of these coordination polymers as revealed in the structure of {[ZnL1Cl 2 ]·1.5H 2 O}n and {[ZnL12 ]·2ClO_4·H_2 O}n, [ZnL2Cl_2·H_2O]n and {[Zn_2 L2_4 (H_2 O)_6 ]·4ClO_4·H 2 O·DMF}n. (4) The hydrogen bonds take an important part in one-dimensional formation of [HL1ClO_4 ]n , [ZnL2Cl_2·H_2 O]n and {[Zn_2 L2_4 (H_2 O)_6 ]·4ClO_4·H_2 O·DMF}n. (5) Silver (I) has various coordination modes and silver (I) cluster has been formed through the bridging of ligand as shown in compound {[Ag_3 L2_2 (H_2O)]·3PF6·4H 2 O}n. Although the anion PF6 - has not coordinated to metal ion, it plays an import role in the formation of 3D.
引文
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