超分子化学是将化学与物理学、材料学、生物学和环境科学等多门学科进行交叉的一门边缘学科，其核心问题是分子识别和组装。分子识别是超分子化学中尤为重要的一项研究领域，也是现代科学发展技术中具有挑战性的热点话题，在光电化学、生物化学、材料化学等方面都有广泛应用。阴离子在自然界中普遍存在，设计合成识别阴离子的受体具有重要意义，其中阴离子识别主要是通过受体分子与阴离子相互作用的结果。本论文进行了吡啶和三甘醇脲类受体的制备、表征及其阴离子结合研究，论述了一种吡啶脲受体及其配合物和两种脲类受体及阴离子结合研究，对制备的化合物进行条件优化、晶体结构解析、各种表征以及与阴离子结合性质的研究。主要工作如下：

（1）制备并表征吡啶脲受体及其配合物

以对氯苯基异氰酸酯和4-吡啶胺为原料，合成了吡啶脲受体L，该配体L与Zn(OAc)₂·2H₂O在甲醇/水条件下进行反应合成了配合物[ZnL₂(OAc)₂]·2H₂O(1)，并对配体和配合物进行了熔点、红外分析、核磁氢谱、单晶结构等表征。X射线单晶衍射分析表明，配体L通过N?H_(脲基)···N_(吡啶基)相互作用和C?H···O相互作用形成了2-D片状网络结构，配合物通过分子间的N?H···O氢键和O?H···O氢键，形成了3-D氢键网络。研究了配体和配合物的热稳定性，结果表明配体的分解需要比配合物更高的表观活化能(E_a)。通过紫外-可见光谱对配体与醋酸根阴离子的结合性质进行了探究。

（2）制备并优化三甘醇脲类受体L^l和L²

以三甘醇、对甲苯磺酰氯、2-硝基苯基异氰酸酯、4-硝基苯基异氰酸酯为主要原料合成了化合物I~IX，并对其中化合物进行了条件优化。制备配体L¹的最佳反应条件：反应温度为75℃，最佳反应时间为3.5 h，原料化合物V 和4-硝基苯基异氰酸酯的最佳反应摩尔比为1:2.2。制备配体L²的最佳反应条件：反应温度为75℃，最佳反应时间为3 h，原料化合物VIII和4-硝基苯基异氰酸酯的最佳反应摩尔比为1:2.2。在制备和条件优化过程中，发明了两种实用新型专利，一种用于平行萃取的实验台架装置和一种利用扩散反应法制备金属配合物单晶的培养装置。

（3）三甘醇脲类配体L^l和L²的各种表征及其与阴离子的结合性质研究

对三甘醇脲类配体L^l和L²及其中间化合物进行了元素分析、红外分析以及核磁共振氢谱分析等表征，实验测定结果与理论结构相一致。通过紫外-可见光谱法对配体与阴离子的结合性质进行探究。对配体L^l和配体L²与各种阴离子进行识别，两种配体对PO₄^3?都有“裸眼识别”的能力，通过紫外-可见光谱可观察到对四面体离子PO₄^3?有较强的识别能力。通过Job曲线，得出配体L²与磷酸根阴离子的结合比为1:1，利用非线性拟合得到配体L²与磷酸根阴离子的结合常数为K_a = 2.75×10⁵ M^-1。

Supramolecular chemistry is a fringe discipline that intersects multiple disciplines such as chemistry, physics, materials science, biology, and environmental science. The core issue is molecular recognition and assembly. Molecular recognition is a particularly important research field in supramolecular chemistry. It is also a challenging hot topic in the development of modern science and technology. It has been widely used in photoelectrochemistry, biochemistry, and material chemistry. Anions are ubiquitous in nature, and it is important to design and synthesize receptors that recognize anions. Among them, anion recognition is mainly the result of the interaction between receptor molecules and anions. In this paper, the preparation, characterization and anion binding studies of pyridine and triethylene glycol urea receptors are discussed. The research of a pyridine urea receptor and its complexes and two urea receptors and anion binding are discussed. Compounds were studied for conditional optimization, crystal structure analysis, various characterizations, and studies on the binding properties with anions. The main tasks were as follows:

(1) Preparation and characterization of pyridylurea receptor and its complex

The pyridylurea receptor L was synthesized using p-chlorophenyl isocyanate and pyridylamine and the complex [ZnL₂(OAc)₂]·2H₂O(1) was synthesized by the reaction of  the ligand L and Zn(OAc)₂·2H₂O under methanol/water conditions, which were characterized by melting point, infrared analysis, nuclear magnetic hydrogen spectroscopy, single crystal structure, etc. X-ray single crystal diffraction analysis showed that the ligand L formed a 2-D network sheet structure by N?H_urea×××N_pyridyl and C?H···O interaction, and the complex 1 possessed a 3-D network extended by intermolecular N?H···O and O?H···O hydrogen bonds. The thermal stability of ligand and complex was studied, and the results showed that the decomposition of the ligand required a higher apparent activation energy (Ea) than that of the complex. The binding properties of the ligand and acetate anion were also investigated by the ultraviolet-visible (UV-vis) spectroscopy.

(2) Preparation and condition's optimization of triethylene glycol urea receptors L¹ and L²

Compounds I to IX were synthesized using triethylene glycol, p-toluenesulfonyl chloride, 2-nitrophenyl isocyanate, and 4-nitrophenyl isocyanate as the main raw materials. The conditions of these compounds were optimized. The best reaction conditions for the synthesis of ligand L¹: the reaction temperature is 75℃, the time is 3.5 h, and the molar ratio of V and 4-nitrophenyl isocyanate is 1:2.2. The optimal reaction conditions for the synthesis of ligand L²: the reaction temperature is 75℃, the time is 3 hours, and the molar ratio of VIII and 4-nitrophenyl isocyanate is 1:2.2. In the process of preparation and optimization of conditions, two utility model patents were invented, an experimental bench device for parallel extraction and a culture device for preparing a metal complex single crystal by a diffusion reaction method.

(3) Characterization of triethylene glycol urea ligands L¹ and L² and the investigation of anion binding properties

The triethylene glycol urea ligands L¹ and L² were characterized by various methods including elemental analysis, infrared analysis and nuclear magnetic resonance spectroscopy analysis, which are consistent with that of the theoretical structures. The recognition properties of ligands with anions were explored by UV-vis spectroscopy. The ligands L¹ and L² are identified with various anions, which show an ability to "recognize PO₄^3? with the naked eye". Through the UV-vis spectra, it can be observed that the tetrahedral PO₄^3? have strong recognition ability. Through the Job curve, the binding ratio of ligand L² to phosphate anion is 1:1, and the binding constant of ligand L² to phosphate anion is K_a = 2.75×10⁵ M^-1 by nonlinear fitting.