Synthesis Of Butanoxy Functional Disulfide Macrocyclic Compounds And Their Application In Titanium Dioxide Modification And Free Radical Polymerization

With the development of science,supramolecular chemistry has gradually become a new chemical discipline,and the development and functional research of macrocyclic host molecules is the focus of supramolecular chemistry research.The appearance of each new macroring greatly enriched the research content of supramolecular chemistry and promoted the continuous development of supramolecular chemistry.In 2000 a new type of supramolecular big ring main body disulfide ring was reported,because of its special molecular structure and based on the dynamic exchange reaction of sulphur-disulfide bond properties has been widely attention and fast speed development,although disulfide macrocyclic development has made gratifying achievements,but there are still many aspects need to dig deep and perfect,such as research system is not yet complete,In this context,it is particularly interesting to study the construction and development of disulfide macrorings in different systems and their application in various fields.Different from previous studies on disulfide macrorings,this work synthesized disulfide macrorings in organic phase system for the first time,and extended the application of disulfide macrorings to photocatalysis and free radical aggregation reaction direction.The main content of this paper mainly includes:（1）Using phloroglucinol as the framework and butyl as the substitution group,the aromatic disulfide compound with alkoxy group was constructed and the catalytic oxidation of sulfhydryl groups to form disulfide bonds was attempted using iodine and dimethyl sulphoxide（DMSO）as catalysts in the organic phase.A ternary disulfide macrocycles（TDSMs）was synthesized with three butyl phenyl ether aromatic disulfide bodies by controlling the concentration of the reaction.Its structure was analyzed by NMR and MS.（2）Doping sulfur into Ti O₂can narrow the bandgap of the native Ti O₂,offering an efficient way to improve its photocatalytic efficiency and extend its absorption from the ultraviolet to the visible light region.However,low doping efficiency has remained a stumbling block in the advanced development of sulfur-doped Ti O₂（S-Ti O₂）.Here,we demonstrated ternary disulfide macrocycles（TDSMs）as ideal candidates for efficiently engineering Ti O₂with sulfur.Inductively coupled plasma atomic emission spectrometry（ICP-AES）analysis showed that the sulfur doping content in the entire S-Ti O₂was about 1.5wt%,while its surface contained about 2.0 wt%sulfur,using only 5.0 wt%DSM as the dopant.The overall utilisation rate of sulfur was determined to be about 95%,which was much higher than those of reported examples.XRD,XPS,FT-IR,UV-Vis,and ICP-AES analyses of the S-Ti O₂material suggested that the sulfur element was in the S⁶⁺form on the crystal lattice by replacing Ti⁴⁺and surface of Ti O₂with the formation of SO₄^2-.The energy bandgap of the S-Ti O₂was 2.3 e V,a reduction compared to the 3.2 e V of native Ti O₂,which allowed the extension of the light absorption range of the engineered material to 700 nm.Accordingly,the materials,loaded with platinum nanoparticles,photo-catalytically split water into hydrogen under visible light.The hydrogen production performance was about 573.3mmol g^-1h^-1（based on the mass of platinum）and remained similar even after 50 h,with a turnover number of 4990.Our findings indicate that ternary disulfide macrocycles（TDSMs）are efficient dopants for modifying Ti O₂with sulfur.The high-efficiency doping of Ti O₂with sulfur from the macrocycles significantly reduced the amounts of dopants needed,presenting a possibility for the green industrial production of S-Ti O₂in the future.（3）Disulfide bond has the properties of low bond energy,easy to break,easy to be reduced by reductants,disulfide bond will occur homolysis under the action of light and oxygen,resulting in sulfhydryl radicals.Based on this,we dissolved the synthesized TDSMs in dichloromethane,made the spontaneous homocleavage of the disulfide bond under the condition of no shading,and precisely controlled the degree of polymerization of sulfhydryl radical,finally formed the quaternary disulfide macroring（QDSMs）.The whole process requires no purification and the conversion rate is close to 100%.It is worth noting that in this process,the quaternary disulfide macroring（QDSMs）appears in the form of single crystal,which provides a better basis for us to analyze the structure and spatial arrangement of the quaternary disulfide macroring（QDSMs）.This study opens up new ideas for the purification of complex disulfide supramolecular chemical systems and radical chemical systems...