【作者】 刘广飞；

【导师】 郎建平；

【作者基本信息】 苏州大学 ， 无机化学， 2008， 博士

【摘要】 由于丰富多彩的结构及在光学、电学、磁性、超导和信息存储等领域巨大的潜在应用前景,众多化学工作者投入到多核配合物和配位聚合物的研究中,其中对这两类配合物的设计和合成是近年来这个领域的研究热点。本论文选择配体2,6-二(3,5-二甲基-N-吡唑)吡啶(bdmpp),用前驱体法及自组装技术得到了系列多核配合物和配位聚合物;选择配体1-氢-1,2,3-三唑-4,5-二羧酸(H3tda),用水热/溶剂热法合成了系列配位聚合物。研究结果简述如下:1.以2,6-二(3,5-二甲基-N-吡唑)吡啶(bdmpp)为配体,在常温下溶液中与金属盐反应,得到一系列单核或双核的小分子配合物。这些配合物都具有潜在的配位能力,可作为较好的前驱体,选择合适的桥联配体进行导向设计和组装多核配合物和配位聚合物。2.选择前驱体[Cu(bdmpp)(MeCN)2][ClO4]2 (2),[Cu(bdmpp)(N3)2]·1.5H2O (8)和[Cu(bdmpp)(N3)(μ-N3)]2·2 MeOH (9)与桥联配体4,4′-bipy,dca-, N3-和ClO4-,以及金属离子M2+ (M = Cu, Co, Ni),设计组装了一系列新的同核和异核多核配合物和配位聚合物{[Cu(bdmpp)(ClO4)]2(μ-4,4′-bipy)}[ClO4]2 (18) ,{[Cu(bdmpp)(μ-dca)][ClO4]}n (19) , {[Cu(bdmpp)(μ-N3)][ClO4]? MeCN}n (20) , {[Cu(bdmpp)(μ-ClO4)][PF6]? (MeCN)}n (21) , [Cu(N3)(bdmpp)]2(μ-N3)2Cu(N3)2 (22)和{[Cu(μ-N3)(bdmpp)(μ-N3)M(μ-N3)(X)]2·eMeCN}n (23 : M = Co,X = N3,,e = 0;24:M = Ni,X = Cl;e = 4)。用元素分析,红外光谱及单晶衍射对配合物18~24进行了表征。配合物18是由4,4′-bipy架桥形成的二聚物;配合物19,20和21则是由dca-,N3-和ClO4-桥联成的一维链状聚合物,其中配合物20和21是一维螺旋链。在配合物22的结构中,其前驱体8的结构和构型都被保留,可以看成是一个平面四边形配位构型的Cu(N3)2片段通过叠氮酸根端基氮原子架桥(μ-1,1)将两个前驱体8的分子连在一起,形成“汉堡包”型三核配合物。同样,在配合物23和24的结构中,前驱体9的分子结构部分[Cu(bdmpp)(μ-N3)(μ-N3)]2被平面四边形配位构型的[M(μ-N3)(X)]2 (23:M = Co,X = N3;24:M = Ni,X = Cl)片段通过叠氮酸根氮原子架桥(23:μ-1,3;24:μ-1,1)形成一维链状结构。另外还用循环伏安法研究了配合物18~24及其前驱体2,8和9的电化学性质。3.配体1,1-二(3,5-二甲基-N-吡唑)甲烷(bdmpm)和2,6-二(3,5-二甲基-N-吡唑)吡啶(bdmpp)与Cu(I)盐或Ag(I)盐在溶液中反应得到三个新的配合物[Cu(bdmpm)2][PF6] (25) , [Cu(μ-bdmpp)(MeCN)]2[PF6]2 (26)和[Ag(μ-bdmpp)NO3]2 (27)。配合物25中Cu(I)是常见的四配位四面体几何构型;配合物26和27中的金属离子[Cu(I)和Ag(I)]虽然也是四面体配位几何构型,但其整个分子的结构则是少见的双金属双螺旋构型。由聚合催化的影响因素和催化的结果可知,配合物25和26催化MMA聚合体系并不是ATRP反应,推测可能是过渡金属配合物发生氧化还原反应时产生的自由基引发的自由基聚合反应。4.利用溶剂热法,以tpt和Cu(I)为原料,合成了一个二维网状结构的配位聚合物{[Cu(tpt)(MeCN)][ClO4]}n (28) [tpt = 2,4,6-三(4-吡啶)-1,3,5-三嗪],此聚合物属于(3,4)-网的范畴,具有(53)2(5482)的拓扑结构;另外还对配合物在固态下的荧光性质进行了研究。5.由于配体1-氢-1,2,3-三唑-4,5-二羧酸(H3tda)的配位点较多,用常规的方法不易得到与金属盐反应生成的配合物,因此选用水热/溶剂热法,在调节pH值及加入辅助配体的条件下,得到了五个配位聚合物29~33。三维聚合物[K2Cd(Htda)2]n (29)属于(4,4,6)-网的范畴,具有(4264)Cd(42638)K(4361082)Htda的拓扑结构;一维链状配合物[Zn2(bpy)2(tda)NO3·0.5H2O]n (30)[bpy = 2,2′-联吡啶]通过较强的辅助配体bpy之间的π···π相互作用形成三维网状结构。[Cu(phen)(Htda)]n (31) (phen = 1,10-邻菲罗琳)和[Cu(bpy)(Htda)]n (33)是在有辅助配体的情况下生成的一维螺旋状聚合物,而配合物32虽然与33在同一条件下得到,但其结构却是一维阶梯状的。另外还研究了配合物29和30及其配体在室温时固态下的荧光性质;对配合物31~33在DMF溶液中进行了循环伏安测试。更多还原

【Abstract】 Considerable efforts are being undertaken to generate multi-dimensional coordination polymers due to their intriguing structural diversities and their potential applications in various advanced materials. The N-containing heterocyclic ligands, 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp) and 1H-1,2,3-triazole-4,5-dicarboxylic acid (H3tda), were chosen in this dissertation to prepare coordination oligomers and polymers through precursor method and hydro-/solvo- thermal methods. The results were summarized as follows:1. 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp) was used to synthesize the transition metal compounds that possess at least one of the following requirements. Firstly, that some ligands around the metal center are labile and be readily replaced by other strong donor ligands. Secondly, that some ligands in the compounds are potential multi-linkers to interconnect with other metal centers. Thirdly, that the coordination is around metal center unsaturated. Such compounds are the potential precursors to generate coordination oligomers and polymers.2. Reactions of three Cu(II) compounds of 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine (bdmpp), [Cu(bdmpp)(MeCN)2][ClO4]2 (2), [Cu(bdmpp)(N3)2]·1.5H2O (8) and [Cu(bdmpp)(N3)(μ-N3)]2·2MeOH (9) with 4,4′-bipy, dicyanamide (dca), azide, or M2+ (M = Cu, Co, Ni) produced a series of homo- and hetero-metallic coordination oligomers and polymers {[Cu(bdmpp)(ClO4)]2(μ-4,4′-bipy)}[ClO4]2 (18), {[Cu(bdmpp)(μ-dca)][ClO4]}n (19), {[Cu(bdmpp)(μ-N3)][ClO4]?MeCN}n (20), {[Cu(bdmpp)(μ-ClO4)][PF6]?(MeCN)}n (21),[Cu(N3)(bdmpp)]2(μ-N3)2Cu(N3)2 (22)和{[Cu(μ-N3)(bdmpp)(μ-N3)M(μ-N3)(X)]2·eMeCN}n (23:M = Co,X = N3,,e = 0;24:M = Ni,X = Cl;e = 4). Compounds 18~24 have been characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray crystallography. Compound 18 has a centrosymmetric dimeric dication structure in which two [Cu(bdmpp)(ClO4)]+ fragments are bridged by one 4,4′-bipy. Compound 19, 20 or 21 has a 1D linear or spiral chain extending along the b-axis in which each [Cu(bdmpp)]2+ fragment links its equivalent ones via bridging dca, azide or perchlorate anions, respectively. Compound 22 has a trinuclear sandwich structure in which two molecules of 8 link a Cu(N3)2 species via two end-on bridging azide anions. Compounds 23 and 24 have a 1D chain structure extending along the c axis in which [Cu(μ-N3)(bdmpp)(μ-N3)M(μ-N3)(X)]2 (M = Co, Ni) molecules are linked by end-to-end azide anions (23) or end-on azide anions (24). In addition, the electrochemical properties of 18~24 and their precurcors 2, 8 and 9 in DMF were also investigated by cyclic voltammetry.3. Three new compounds, [Cu(bdmpm)2][PF6] (25) [bdmpm = bis(3,5-dimethyl-N-pyrazolyl) methane], [Cu(μ-bdmpp)(MeCN)]2[PF6]2 (26) and [Ag(μ-bdmpp)NO3]2 (27) [bdmpp = 2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine], were prepared directly by metal salts and ligands. X-ray analysis revealed that compounds 26 and 27 are metal ion-induced double-stranded helicates that are bridged by the twisted bdmpp ligands. Compounds 25 and 26 were employed as catalysts in the ATRP of MMA in cyclohexanone, while compound 27 failed to work in the polymerization of MMA even using initiator. Though MMA was polymerized in the presence of compounds 25 and 26, as well as initiator (EBiB), it did not belong to the system of ATRP. The effects of the polymerization temperature and the various ratios of MMA to Cu(I), as well as solvent were investigated in details only in the presence of compound 25 or 26 as catalysts.4. The solvothermal method was employed to prepare a novel copper(I) coordination polymer, {[Cu(tpt)(MeCN)][ClO4]}∞(28) [tpt = 2,4,6-tris(4-pyridyl)-1,3,5-triazine]. Single crystal X-ray diffraction showed that the compound 28 consists of a 2D (3,4)-connected network with a unique (53)2(5482) topology. The luminescent properties of compound 28 in the solid state at ambient temperature were investigated.5. Five novel cadmium(II)/Htda, zinc(II)/tda and Cu(II)/phen(bpy)/Htda coordination polymer [K2Cd(Htda)2]n (29) (H3tda = 1-H-1,2,3-triazole-4,5-dicarboxylate), [Zn2(bpy)2(tda)NO3·0.5H2O]n (30) (bpy = 2,2′-bipyridine), [Cu(phen)(Htda)] (31), [Cu(bpy)(Htda)] (blue)(32) (phen = 1,10-phenanthroline) and [Cu(bpy)(Htda)] (light blue) (33) were prepared through solvothermal methods and structurally characterized. An X-ray analysis revealed that 29 consists of an unusual 3D (4,4,6)-connected network with a (4264)Cd(42638)K(4361082)Htda topology; compound 30 is a 1D chain structure and then connected byπ···πinteraction between auxiliary ligand of bpys to form a 3D net. The luminescent properties of compounds 29 and 30 along with the H3tda ligand in the solid state were investigated. Compound 31 or 33 has a 1D spiral chain structure and compound 32 has a 1D stair-like chain structure, and their electronic properties were determined by cyclic voltammetry.更多还原