摘要配位分子簇作为多样化和可设计的金属-有机配位体系，可以通过设计和调

Summary of <br>ligand diversification molecular cluster and can be designed as a metal - organic coordination system can be regulated by designing and organic ligands and metal ions, as their function as light, magnetic fields, and catalytic loading and modified. As a material system with precise structural information, the chemical bonding, spatial structure and interaction of coordination molecular clusters at the atomic and molecular levels will not only help understand the structure-activity relationship of materials, but also hopefully direct their specific functions. Design and improvement. More and more chemists are devoted to the pursuit of novel structure design and rich performance of coordination molecular clusters, which has promoted the rapid development of coordination molecular clusters in the field of coordination chemistry. However, how to fully combine the advantages of coordination molecular clusters in structural design, further expand its functionalization and derivatization within the scope of interdisciplinary, and use this as a basis to develop its functional design and application expansion in frontier fields is still current Scientific problems that need to be solved urgently. In this thesis, a cubane nickel cluster with the "M4L3" configuration was designed and synthesized with an o-vanillin Schiff base ligand, and the stability of the cluster was explored based on the information of its solid-liquid structure, and its role in electrocatalytic production was investigated. The application of oxygen and electrocatalytic urea oxidation. Finally, the electrocatalytic reaction mechanism was explored through theoretical calculations; a series of cobalt-based and cobalt-nickel doped clusters based on cubane structural units were constructed, through X-ray diffraction and electrospray The combined method of mass spectrometry (ESI-MS) explored its solid-liquid structure information and expanded its application in electrocatalytic oxygen production and electrocatalytic urea oxidation. The full text is divided into three chapters: The <br>first chapter is the introduction, which summarizes the research background and scientific challenges of the electrocatalytic oxygen evolution reaction (OER) and the electrocatalytic urea oxidation reaction (UOR). Secondly, the current coordination molecular clusters are analyzed. Important progress and advantages in the field of energy storage and conversion research, and the application of cubane molecular clusters in catalysis, and finally combined with the research team’s good foundation in the design, assembly process, mechanism research and functional exploration of coordination molecular clusters. The significance of the thesis topic selection.<br>The second chapter introduces the synthesis of the "M4L3" configuration of cubane tetranuclear nickel clusters by selecting 3-(2-hydroxy-3-methoxybenzylidene) imino-1, 2-propanediol (H3L) { [[Ni4(HL)3(CH3O)(CH3OH)3](CH3COO)]} (Compound 1). Through the combination of electrospray mass spectrometry (ESI-MS) and X-ray single crystal diffraction, the structural characteristics of compound 1 were studied by using its solid-liquid structure information. The organic ligands outside the cubane molecular clusters protect the core structure of the cluster to make it have high The stability, easy-to-leave coordination solvent molecules can fully expose the active sites to ensure the high catalytic activity of the catalyst. At the same time, the catalyzed sample compounds 2 and 3 of compound 1 under different catalytic conditions were obtained through recrystallization. A series of characterizations proved that the cubane core of sample 1 did not change before and after the catalysis, and only the coordination solvent was replaced. It confirms our inference of structural information. In addition, compound 1 can be used as an effective OER and UOR catalyst. In a 1.0 M KOH electrolyte solution, the Ni4 sample achieves an overpotential of 320 mV at a current density of 10 mA cm-2, when in a 1 M KOH+0.33M solution The high-efficiency UOR activity is shown in, the overpotential corresponding to 10 mA cm-2 is only 1.337 V, and the maximum current density is 310 mA cm-2. The catalytic performance of UOR is better than most catalysts that have been reported, and within 20 hours High stability is maintained inside. Finally, based on the DFT calculation results, a single-site catalytic mechanism for the OER and UOR reactions is proposed, which not only ensures high catalytic efficiency, but also avoids the structural damage and deactivation of the catalyst. As far as we know, Ni4 is the first coordinating molecule cluster-based bifunctional electrocatalyst with both high-efficiency OER and UOR activity. We have achieved a win-win situation between stability and catalytic activity, and created a new preparation for single-site catalysts. The strategy is expected to contribute to the development of new efficient and stable molecular cluster catalysts in the future.<br>Chapter 3 introduces the in-situ generation of Schiff base ligands based on 3-methoxy salicylaldehyde and 3-amino-1, 2-propanediol and the synthesis of two coordination molecules with cubane or vacant cubane configuration. Cluster: [Co4(HL)4] (Compound 2), [NixCo8-x(L)3(HL)3(CH3O)(H2O)3] (Compound 5). Two molecular clusters with different structures show common structural features: 1) the organic ligands are multidentate chelated to connect multiple metal ions; 2) the peripheral organic ligands surround the cluster core to protect the key core structure. Further through the solid-liquid structure information correlation, powder diffraction after soaking in strong alkaline electrolyte reveals that the encapsulation of organic ligands from the periphery makes the molecular clusters have strong stability. Compound 4 exhibits high-efficiency OER performance in 1 M KOH solution, and has a smaller overpotential in the reported coordination molecular cluster-based electrocatalysts, which is a new function expansion of coordination molecular clusters and new system development of energy materials. It provides new perspectives and ideas to realize the precise design of chemistry to the controllable synthesis of material systems.

Summary<br>As a diversified and designable metal-organic mating system, mating molecular clusters can be functionally loaded and modified in areas such as luminescence, magnetism and catalysis by designing and regulating organic compounds and metal ions. As a material system with precise structural information, the chemical bonding, spatial structure and interaction of mating molecule clusters at the atomic and molecular levels not only help to understand the material's structure relationship, but also hope to design and improve the orientation of its specific functions. More and more chemists are devoted to the design and rich performance of the novel structure of mating molecular clusters, which has promoted the rapid development of mating molecular clusters in the field of mating chemistry. However, how to fully combine the advantages of mating molecular clusters in structural design, further expand its functionalization and derivation within the scope of interdisciplinary disciplines, and on this basis to develop its functional design and application expansion in the frontier areas is still an urgent need to solve the scientific problem. This paper synthesizes cubic alkane nickel clusters with "M4L3" configuration by designing and synthesizing the adjacent vanilla aldehyde schiff alkali ligand, and explores the stability of the cluster in combination with its solid-liquid structure information, and explores its application in electro-catalytic oxygen production and electro-catalytic urea oxidation. Finally, the electro-catalytic reaction structure is probed by theoretical calculation, a series of cobalt-based and cobalt-nickel doping clusters based on cubicane structure units are constructed, and the solid-liquid structure information is probed by combining X-ray diffraction with electrosol mass spectrometretography (ESI-MS). and expanded its application in electro-catalytic oxygen production and electro-catalytic urea oxidation. The full text is divided into three chapters:<br>The first chapter is the foreword, which summarizes the research background and scientific challenges of the material system of electro-catalytic oxygen reaction (OER) and electro-catalytic urea oxidation reaction (UOR), followed by an analysis of the important progress and advantages of the current distribution molecular cluster in the field of energy storage and conversion research, and the application of cubicane molecular cluster in catalysis, and finally, combined with the project group in the design, assembly process and mechanism of the distribution molecular cluster and its functional exploration of the good foundation, put forward the paper selection significance.<br>The second chapter describes the cubic alkaloid four-core nickel cluster ((NI4(HL) 3 (CH3OH) (CH3OH) 3 (CH3COO)) (compound 1) by selecting 3-(2-hydroxyl-3-methyl-acetyla) subaminoid-1, 2-propylene glycol (H3L) configuration. The structural characteristics of compound 1 are studied by combining electrosumatic mass spectrometry (ESI-MS) and X-ray monocrystalline diffraction, and the organic ligand protection core structure outside the cubicane molecular cluster makes it highly stable, and the easy-to-leave mating solvent molecule can make the active bits fully exposed to ensure the high catalytic activity of the catalyst. At the same time, through recrystrystry obtained compound 1 catalytic sample compound 2 and compound 3 under different catalytic conditions, through a series of characterization to prove that the cubicane core of sample 1 before and after catalysis has not changed, only the replacement of the distribution solvent, confirmed our inference of structural information. In addition, compound 1 can be used as an effective OER and UOR catalyst, in a 1.0 M KOH electrolyte solution, ni4 samples at a current density of 10 mA cm-2 to achieve a cross potential of 320 mV, at 1 M KOH plus 0 The .33M solution shows efficient UOR activity, with an overcurrent of only 1.337 V for 10 mA cm-2 and a maximum current density of 310 mA cm-2, and UOR's catalytic properties are better than most reported catalysts. And in 20 hours to maintain a high degree of stability. Finally, according to the DFT calculation results, the unit point catalysis of OER and UOR reactions is proposed, which not only guarantees the high catalytic efficiency, but also avoids the catalyst structure double damage and inactive. As far as we know, Ni4, as the first two-functional electrocatalyst with high-efficiency OER and UOR activity, achieves a win-win situation between stability and catalytic activity, and creates a new strategy for the preparation of single-center catalysts, which is expected to contribute to the development of new high-efficiency and stable molecular cluster catalysts in the future.<br>The third chapter introduces the mating molecular clusters based on 3-methoxygenated sewerial aldehyde and 3-amino-1, 2-propylene glycol in-place to generate Shiv alkali ligations and synthesizes two cubic or missing cubicane configurations: Co4 (HL) 4 (compound 2), NixCo8-x (L) 3 (HL) 3 (CH3O) (H2O) 3 (compound 5). The molecular clusters of two different structures show common structural characteristics: 1) organic ligand multi-tooth chelation connects multiple metal ions, and 2) peripheral organic ligands surround cluster cores to achieve the protection of key core structures. Further through solid-liquid structure information correlation, strong alkaline electrolyte soaked powder diffraction revealed that the package from the peripheral organic compound makes the molecular cluster have a strong stability. Compound 4 shows the highly efficient OER performance in 1 M KOH solution, has the smaller over-potential in the distribution molecular cluster-based electrocatalyst currently reported, provides a new perspective and idea for the new function expansion of the mating molecular cluster, the development of the new system of energy materials, and the realization of controlled synthesis from the precise design of chemistry to the material system.

abstract<br>As a diverse and designable metal organic coordination system, coordination clusters can be loaded and modified in the fields of luminescence, magnetism and catalysis by designing and regulating organic ligands and metal ions. As a material system with precise structural information, the chemical bonding, spatial structure and interaction of coordination molecular clusters at the atomic and molecular levels are not only helpful to understand the structure-activity relationship of materials, but also to design and improve their specific functions. More and more chemists are devoted to the design of novel structures and the pursuit of rich properties of coordination clusters, which promotes the great development of coordination clusters in the field of coordination chemistry. However, how to fully combine the advantages of coordination molecular clusters in structural design, further expand their functionalization and derivatization in the interdisciplinary scope, and develop their functional design and application in the frontier field on this basis is still an urgent scientific problem to be solved. Finally, the mechanism of catalytic oxidation of o-alkanol with cubic Schiff base was explored Cobalt and nickel doped clusters were investigated by means of X- ray diffraction and electrospray ionization mass spectrometry (ESI-MS). Their solid-liquid structure information was explored, and their applications in electrocatalytic oxygen production and electrocatalytic urea oxidation were also expanded. This paper is divided into three chapters<br>In the first chapter, the research background and scientific challenges of electrocatalytic oxygen evolution reaction (OER) and electrocatalytic urea oxidation reaction (uor) are summarized. Then, the important progress and advantages of current coordination molecular clusters in energy storage and conversion are analyzed, and the application of cubane cluster in catalysis is discussed. Finally, the design and assembly of coordination molecular clusters are discussed It is a good foundation for the research of mechanism and function of Cheng He, and the significance of topic selection is put forward.<br>In the second chapter, the "m4l3" tetranuclear nickel cluster {[[Ni4 (HL) 3 (CH3O) (CH3OH) 3] (CH3COO)]} (compound 1) was synthesized by selecting 3 - (2-hydroxy-3-methoxybenzylidene) imino-1,2-propanediol (H3L). The structural characteristics of compound 1 were studied by means of electrospray ionization mass spectrometry (ESI-MS) and X- ray single crystal diffraction. The organic ligand protection structure of cuboid clusters outside the cuboid cluster has high stability, and the solvent molecules that are easy to leave can sufficiently expose the active sites to ensure the high catalytic activity of the catalyst. At the same time, compound 2 and compound 3 of compound 1 were obtained by recrystallization under different catalytic conditions. Through a series of characterization, it was proved that the cubane core of sample 1 did not change before and after catalysis, but only the replacement of coordination solvent, which confirmed our inference of structural information. In addition, compound 1 can be used as an effective oer and uor catalyst. In 1.0 m KOH electrolyte solution, Ni4 sample achieved 320 MV overpotential at 10 Ma cm-2 current density, and showed efficient uor activity in 1 m KOH + 0.33 M solution. The overpotential corresponding to 10 Ma cm-2 was only 1.337 V, and the maximum current density was 310 Ma cm-2 The catalytic performance of uor was better than that of most of the reported catalysts, and it maintained high stability within 20 hours. Finally, according to the DFT calculation results, the unit point catalytic mechanism of oer and uor reactions is proposed, which not only ensures the high catalytic efficiency, but also avoids the deactivation due to the destruction of catalyst structure. As far as we know, as the first coordination cluster based bifunctional electrocatalyst with high oer and uor activity, Ni4 has achieved a win-win situation between stability and catalytic activity, and created a new strategy for the preparation of single center catalysts, which is expected to contribute to the development of new efficient and stable cluster catalysts in the future.<br>In the third chapter, two coordination clusters [Co4 (HL) 4] (compound 2), [nixco8-x (L) 3 (HL) 3 (CH3O) (H2O) 3] (compound 5) were synthesized based on the in-situ formation of Schiff base ligands from 3-methoxysalicylaldehyde and 3-amino-1,2-propanediol. The two clusters with different structures show common structural features: 1) the organic ligands are multi dentate chelated to connect multiple metal ions; 2) the peripheral organic ligands surround the cluster core to protect the key core structure. Furthermore, the solid-liquid structure information correlation and the powder diffraction after immersion in strong alkaline electrolyte reveal that the organic ligands from the periphery make the clusters have strong stability. Compound 4 shows high oer performance in 1 m KOH solution, and has a small overpotential in the reported coordination molecular cluster based electrocatalyst, which provides a new perspective and idea for the development of new functions of coordination molecular clusters, the development of new energy materials systems, and the realization of precise chemical design and controllable synthesis of material systems.<br>