Solvothermal In Situ Organic Reactions And Physical Properties Of The Inorganic-Organic Hybrid Products

Solvothermal in situ organic reactions refer to the processes including the generation of new organic compounds, combination of the newly generated organic compounds with metal ions, and crystallization of the inorganic-organic hybrid compounds under solvothermal conditions. From the perspective of organic chemistry, under the relatively high temperature and pressure solvothermal reaction conditions, some reactions that can not take place or proceed slowly under conventional reaction conditions, may proceed smoothly and generate the unique organic products. On the other hand, from the perspective of inorganic chemistry, the functional inorganic-organic hybrid compounds can be obtained in one pot via solvothermal in situ organic reactions, and specially, some products can not be formed through other synthetic methods including common solvothermal approach.Since the discovery of the first solvothermal in situ organic reaction, this research subject has experienced a short period of only more than ten years of development. However, rapid progress has been received, and to date, over twenty solvothermal in situ organic reactions were found and a number of inorganic-organic hybrid products with intriguing structures and different kinds of physical properties were gotten. It can be predicted that, solvothermal in situ organic reactions will play an active role in promoting scientific and technological progress as well as the improvement of living and production levels of human beings. Frankly, as an emerging discipline that blending the inorganic chemistry and organic chemistry, there are too many unknown things to be explored, and a lot of valuable discoveries to be further studied and applied.In this thesis, we focused on four types of solvothermal in situ organic reactions: synthesis of low dimensional halometallate-pyridinium inorganic-organic hybrid compounds by using alcohols as alkylation reagents under solvothermal conditions; synthesis of sulfur-containing coordination polymers based on the transformation of 4,4’-dipyridyl disulfide under solvothermal conditions; synthesis of cluster-based coordination polymers by means of the amination reactions of iodobenzene with inorganic ammonia under solvothermal conditions; synthesis of functional silver(I) and cobalt(II) coordination polymers containing multidentate tetrazole ligands via the [3+2] cycloaddition reactions of azide to nitrile under solvothermal conditions. Furthermore, we investigated the crystal structures and explored the physical properties including conductivity, permittivity, third-order nonlinear optical properties, photoluminescent properties and magnetic properties. The research results are briefly described as follows.1. Under solvothermal conditions, the in situ organic reactions of metal halide, alcohols and 4,4’-bipyridine or 4-cyanopyridine in the presence of iodine and a small amount of water produced a series of crystalline low-dimensional halometallate-pyridinium inorganic-organic hybrid compounds, in which the organic pyridinium cations were generated via the combination of pyridyl groups and alkyl part of alcohols. We not only studied the traditional semiconducting properties of the crystalline products, including temperature dependence of the electrical conductivity, frequency dependence of the electrical conductivity, and the impact of doping on the electrical conductivity, but also explored the dielectric properties of them. The results showed that these halometallate-pyridinium hybrids featured their relatively low dielectric constant values. According to the relationship between structures and properties, it was found that the dielectric constant values might strongly relate with the electrostatic interactions in the crystals.2. Based on the transformation of 4,4’-dipyridyl disulfide under solvothermal conditions, a series of sulfur-containing coordination polymers were generated in situ. Thereinto, the Cu/S/I-based hybrid products only showed the interesting time effects in their preparation processes, but also exhibited the unique semiconducting properties compared with the pure Cu2S and CuI semiconductors. In addition, we obtained some other functional sulfur-containing coordination polymers with intriguing structures, such as noncentrosymmetric structures and chiral coordination polycatenane structures. Likewise, their corresponding third-order nonlinear optical properties and photoluminescent properties were explored. 3. We confirmed the feasibility of the amination reactions between iodobenzene and inorganic ammonia under solvothermal conditions, and synthesized a series of Cu/I cluster-based supramolecular coordination polymers. The amination product, aniline, served as the organic template and induced the formation of Cu/I cluster-based supramolecular coordination polymers with different configurations to some extent. Fluorescence studies showed that the products exhibited strong and characteristic photoluminescent behaviors.4. Based on the [3+2] cycloaddition reactions of azide to nitrile under solvothermal conditions, a series of functional silver(I)-tetrazole and cobalt(II)-tetrazole coordination polymers were generated in situ by using silver(I) salt and cobalt(II) salt as Lewis acid catalyst. At the same time, their corresponding photoluminescent properties and magnetic properties were investigated.