Design,Assembly And Photo-Electro-Magnetic Properties Of Sulfur-Containing Functional Molecules

The material formed by the assembly of sulfur-containing functional molecules is a sulfur-containing functional material.Such functional materials have specific optical,electrical,magnetic,and acoustic properties in practical applications,and can satisfy the application of proton conduction,electron conduction,and magnetic materials.Therefore,design and synthesis of new sulfur functionalized molecules is the focus of researchers.This thesis mainly designs different sulfur-containing functional molecules.Based on the existing research,three different sulfur-containing functional materials are prepared by assembling functional molecules.Using different characterization methods,the structure and properties are studied.The specific research content is divided into three parts:First,a triangular open organic ligand L1 is designed and synthesized which contains six thioester functional groups.A two dimensional covalent metal organic frameworks is prepared by in situ hydrolysis.The material is not only structurally porous,but also has better stability than others frameworks,which metal ions and sulfur atoms are combined by a covalent bond.In terms of electrical conductivity.The material has a room temperature conductivity of 3.86×10^-44 S/m,indicating that it has good electronic conductivity.Second,a thiol-functionalized phthalocyanine L2 molecule is synthesized.The sulfur-functionalized phthalocyanine precursor molecules were prepared by pre-introduction of long chain alkane and thiol protecting groups prior to the formation of phthalocyanine.Subsequently,the material is assembled to form a sulfur-functionalized phthalocyanine molecule L2,and at the same time,the problem that the solubility of the phthalocyanine in the organic solvent is poor and the thiol functional group is difficult to introduced into the phthalocyanine is solved.After the formation of the phthalocyanine,the thiol protecting group can be deprotected by mild means to obtain the thiol-functionalized phthalocyanine molecule L2.The molecule is detected by a free radical signal at room temperature,which may enhance the conductivity of the material.Further,by controlling the ratio of the reaction raw materials,another type of sulfur-containing functionalized metal phthalocyanine molecule L3 is obtained.The properties of the L3 heat-treated product were investigated.The magnetic behavior of the product changed with the heating time or the temperature increased,and the electrical conductivity increased.Finally,the thiol functional group in the metal organic framework material is oxidized by a post-synthesis modification method to obtain a sulfonic acid type metal organic framework material UiO-66-SO₃H.It was then immersed in a 5%potassium permanganate aqueous solution to obtain a sample of UiO-66-SO₃H-KMnO₄.It is known from powder diffraction that there is no significant change in the structure of the frameworks before and after immersion,and further related magnetic characterization is performed.The second part is to modify the thiol-containing organic ligand H₂DMBD to synthesize the S-CH=CH₂ ligand L4.The metal organic framework material UiO-66-SCH=CH₂ was prepared by the coordination of L4 with the metal ion Zr⁴⁺.The solid fluorescence characterization of the ligand and MOFs showed that the fluorescence emission peak（502 nm）of MOFs showed a blue shift phenomenon compared with the fluorescence emission peak（526 nm）of the ligand.It is inferred that the luminescence mechanism is that after the double bondπbond on the ligand absorbs light energy,the ground state electrons transition to the excited state,undergoes photo-physical reaction such as vibration relaxation,and finally releases in the form of light.