【作者】 尹明彩；

【导师】 孙聚堂；

【作者基本信息】 武汉大学 ， 无机化学， 2004， 博士

【摘要】 近年来，关于配位聚合物晶体材料的设计、合成、结构及性能研究十分活跃。除了应用较多的吡啶杂环类配体外，芳香羧酸类配体也因具有一系列的特性而被广泛用于配位聚合物的构筑，但所用的合成方法多为常规溶液合成法和水（溶剂）热法。流变相反应法，作为本课题组提出的一种新的软化学合成法，具有反应条件温和、反应速度快、操作简便等优点，已被成功用于一系列功能材料（如锂离子电池正、负极材料等）的制备。然而，对将该方法应用于单晶制备方面的研究还很少。 本论文主要在运用流变相反应法制备芳香羧酸配合物单晶方面进行了有意义的探索。以氧化锌或氯化锶、稀土氧化物或氯化物、芳香羧酸（苯甲酸、水杨酸、α-呋喃甲酸、α-噻吩甲酸、均苯四甲酸）及邻菲罗啉为原料，通过流变相体系中反应物分子之间的分子识别和自组装作用得到了一系列尚未见文献报道的芳香羧酸配合物或配位聚合物，拓展了该反应方法的应用范围，并为单晶制备提供了一种新方法。对这些配合物的晶体结构进行了解析，并对其光谱性能进行了研究，对物质结构与发光性能间的关系进行了探讨。主要研究成果如下： 1．合成了具有强绿色发光的一维配位聚合物{[Tb（FUR）₃（H₂O）₂]·DMF}_n。在该配合物中，每个Tb原子处于八面体配位环境中，相邻Tb原子间通过呋喃甲酸配体桥联成一维链状结构。DMF分子未参与配位，仅通过分子间氢键与一维链相连。氢键及芳香堆积作用将一维链连成二维层状结构。 2．以氯化锶、氯化铽、水杨酸及邻菲罗啉为原料，合成了新型的离子型水杨酸铽二聚物[Tb₂（Hsal）₈（H₂O）₂][（Hphen）₂]·2H₂O。实验中发现Sr²⁺的存在对该配合物单晶的生长具有调控作用。在该配合物中，[Tb₂（Hsal）₈]^2-单元间通过分子间氢键相连成一维链状结构，[Hphen]⁺位于一维链的两侧。phen环平面与水杨酸配体苯环平面间的π-π芳香堆积作用进一步将一维链连成二维层。在紫外光激发下，该配合物发出强的绿色荧光，但较差的能级匹配使得该配合物的荧光强度显著低于二元配合物Tb（Hsal）₃（H₂O）₂·2H₂O。 3．得到了两个具有新颖结构和强红色荧光的离子型二聚物[Eu₂（Hsal）₈][Zn（phen）₃]-（H₂sal）（H₂O）（2-1）和[Eu₂（TPA）₈][Zn（TPA）（phen）₂]₂·（H₂O）₂（2-2）。值得注意的是，在配合物2-1中存在两类[Eu₂（Hsal）₈]^2-二聚单元，Eu1为八配位，Eu2为九配位。水杨酸配体和结晶水间的弱分子间氢键将Eu1二聚单元连成一维链状结构。配合物2-2中的【Eu₂（TPA）₈]^2-单元与配合物2-1中的Eu1单元相类似，但反应条件的不同却使得两配合物中Zn²⁺离子周围的配位环境发生了显著改变。 4．合成、表征了三个Ln-Zn四核异金属配合物Tb₂Zn₂（Bzo）₁₀（phen）₂（3-1）、Tb₂Zn₂（TPA）₁₀（phen）₂（3-2）和Eu₂Zn₂（Bzo）₁₀（phen）₂（3-3）。配合物3-1与配合物3-3的晶体结构基本相同。但羧酸配体的改变对Tb的配位环境产生显著影响：在配合物3-1中，Tb为八配位，而在配合物3一2中，Tb仅为七配位。在紫外光的激发下，配合物3一1和3一2均发出强的绿色荧光，配合物3一3发出强的红色荧光。荧光光谱测定发现:zn2+离子及邻菲罗琳的引入均可显著增强配合物的荧光。 5.高选择性的得到了两个具有良好溶解性能的Ln一Zn异金属一维配位聚合物【z，ILnZ（FUR）;。（HZo）2]。（Ln二Eu、Tb）。两配合物的晶体结构基本相同，zn、Ln间通过吠喃甲酸配体相互桥联成一维链状结构。Zn、Ln的排列顺序为忆n-Ln--Ln，Zn--Ln-Ln--。在紫外光激发下，二者的固体样品分别发出强的铺或试的特征荧光。然而，与二元吠喃甲酸配合物相比，z矛+离子的引入对配合物的荧光无明显影响。两配合物良好的溶解性能为其在电致发光方面的应用提供了可能。 6.为了研究配合物的结构与发光性质间的关系，采用常规溶液反应法得到了一维配位聚合物[E u（H2sal）（Hsal）（sal）.H2o]n。通过对该配合物与其它稀土芳香梭酸配合物的结构进行对比，提出了关于能量传递的新观点，发现该物质区别于其他芳香梭酸配合物的独特一维带状结构是导致其不发光的主要原因。 7.在运用流变相反应法制备芳香梭酸配合物的过程中，得到了一个新型的质子转移盐型配合物（H4BTEC）[HZBTEC』[Hphen』2。该配合物由均苯四甲酸分子、均苯四甲酸阴离子和邻菲罗琳阳离子构成。均苯四甲酸分子与均苯四甲酸阴离子间通过分子间氢键相连成二维层状结构，[H phen]+离子位于该层的两侧并通过分子间氢键与其相连。在紫外光激发下，该配合物发出较强的蓝紫色荧光。 8.通过苯甲酸锌惰性气氛下的热解，得到了溶解性能良好、结构新颖的四核苯甲酸锌配合物Zn4O（C6HsCOZ）6。该化合物具有不常见的较大晶胞参数:a=41 .o063（18）A，犷一68953（5）矛，z二48。在该化合物中，四个zn原子通过中心氧原子相连成一正四面体。每一个Zn原子呈略扭曲的四面体构型，整个Zn4O（C 6HSCOZ）6分子呈畸变的八面体构型。该配合物中存在一系列不相交叉的平行孔道和大量的孔洞。这些孔道和孔洞有可能可以吸附如水、苯等小分子，使得该化合物在微孔材料方面具有潜在的应用前景。在紫外或可见光的激?更多还原

【Abstract】 In recent years, much attention has been paid to the design, syntheses, crystal structures and properties of coordination polymers. Besides the extensive application of nitrogen-containing heterocyclic ligands, such as 4,4’-bipyridine, aromatic carboxylic acids, owing to their unique characteristics, have also been used in the construction of coordination polymers. However, the methods usually used are conventional solution and hydro(solvo)thermal reaction methods. Rheological phase reaction method, as a new soft chemistry synthetic method put forward by our laboratory, has been successfully applied in the preparation of many functional materials, such as the positive and negative electrode materials of lithium ion secondary battery. This method has many advantages, for example, the reaction condition is mild, the reaction time is short and the operation is very simple. However, the researches on its application to the preparation of single crystals are still rare.In this research, valuable explorations about the application of rheological phase reaction method to the preparation of aromatic carboxylate single crystals were carried out. With zinc oxide or strontium chloride, lanthanide oxide or chloride, aromatic carboxylic acids (benzoic acid, salicylic acid, ct-furancarboxylic acid, a-thiophenecarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid) and 1,10-phenanthroline, a series of novel aromatic carboxylate complexes or coordination polymers were obtained through the molecular recognition and self-assembly of the reactants in the rheological phase system, which open a new way for this synthetic method and offer a new method for single crystal growth. Their crystal structures and spectral properties were characterized. The relationship between crystal structures and luminescent properties were discussed. The main results are as follows:1. An 1-D coordination polymer {[Tb(FUR)3(H2O)2]-DMF}n with intense green luminescence was synthesized, in which each Tb atom is eight-coordinated and the adjacent Tb atoms are linked into 1-D chains through bridging furancarboxylate ligands. The DMF molecules do not coordinate to the Tb atom and are linked to the 1-D chains through intermolecular hydrogen bonds. These 1-D chains are connected into 2-D layers through hydrogen bonds and π-π aromatic stacking interactions.2. A novel ionic dimer [Tb2(Hsal)8(H2O)2][(Hphen)2]-2H2O was synthesized from SrCh, TbCb, salicylic acid and 1,10-phenanthroline. During the experiment, it was found that the existence of Sr2+ plays a control role in the crystal growth. In this complex, the dimeric [Tb2(Hsal)8(H2O)2]2- anions are linked into 1-D chains by intermolecular hydrogen bonds. The mono-protonated [(Hphen)2]+ cations are located on the both sides of the 1-D chains. The π-π stacking interactions between the phen molecules and the benzene rings of salicylate ligands link the 1-D chains into 2-D layers. When irradiated by UV light, it emits intense green luminescence of Tb3+ ions, however, due to the energy mismatch, its luminescentIIIintensity is lower than that of the binary complex Tb(Hsal)3(H2O)2-2H2O.3. Two ionic dimeric complexes with novel crystal structures and strong red luminescence were obtained. It is worth to note that in [Eu2(Hsal)8][Zn(phen)3]-(H2salXH2O) (2-1), there are two independent dimeric [Eu2(Hsal)8]2" anions. Eul is eight-coordinated and Eu2 is in a nine-coordination environment. Weak intermolecular hydrogen bonds formed between the salicylate ligands and the lattice water molecules link the dimeric Eul anions into 1-D chains. In [Eu2(TPA)8][Zn(TPA)(phen)2]2-(H2O)2(2-2), the coordination environment of Eu3+ ion is the same as that of Eul in complex 2-1. While in these two complexes the coordination geometries around the Zn atoms are obviously different because of the different reaction conditions.4. Three Ln-Zn tetranuclear heterometallic complexes Tb2Zn2(Bzo)io(phen)2 (3-1), Tb2Zn2(TPA)io(phen)2 (3-2) and Eu2Zn2(Bzo)io(phen)2 (3-3) were synthesized and charact更多还原