The Synthesis Of CIE Small Organic Molecules Containing Hydrazone Structure And Functional Polysulfates

Over the past few decades,small molecules or polymers with Aggregation Induced Light Emitting(AIE)effects have received great attention and development due to their superiority in organic optoelectronic materials,solid fluorescent materials,multi-stimulus response materials,and various sensors.The design of AIE or CIE molecules has always been a hot pursuit for researchers,but the structural characteristics and luminescence mechanism of molecules with the CIE phenomenon are few.Therefore,the exploration of new CIE chromophores is of great significance.On this basis,it is of great value to introduce organic small molecules with AIE effect into polymer chains.It is worth mentioning that the use of the Su FEx click chemistry reaction reported by the Sharpless group in 2014 caused a huge scientific research trend.Through this simple,quick and green click chemistry,it is possible to synthesize polysulfates with good thermal stability,corrosion resistance,and resistance to oxidation and reduction.A series of functional polysulfates can be obtained through the Su FEx Click Chemistry for small molecules or polymers with special functional groups.This method provides new ideas for the synthesis and modification of biomedicines,photoelectric materials,functional polymers,etc.At the same time,it has brought hope for the industrialization of sulfates.The main work of the dissertation includes the following aspects: 1)Coupling of a compound containing a naphthalimide functional group with a compound of an aldehyde phenolic group was successfully used to obtain two similar "butterfly-like" organic molecules containing diterpenoids(NA-1BA and NA-3BA).These two small molecules exhibit a special crystallization-induced luminescence effect in the crystalline state.A number of amorphous and crystalline samples were prepared by grinding,solvent fumigation or poor-solvent aggregation,and the fluorescence of different crystalline samples was examined.Crystalline samples exhibited intense fluorescence while amorphous samples were almost non-fluorescent.Single crystal analysis and theoretical calculations show that the luminescence of the crystalline sample is mainly due to the accumulation of intermolecular hydrogen bonds that restricts intramolecular rotation and vibration,thereby significantly enhancing the radiative transition of the crystalline state.2)Using a simple Suzuki reaction,a benzothiadiazole-containing fluorescent small molecule(DTBT)was synthesized and three different crystal forms of the compound were prepared under different conditions.The photophysical properties of different solvents were investigated.The differences in the luminescent properties of different crystalline samples were stuied by XRD and solid-state fluorescence measurements.3)Two polysulfates containing a fluorescent chromophore(pyrazoline-naphthalimide)were designed and synthesized by the new Suf Ex hexafluoride-sulfur exchange(Su FEx)proposed by Sharpless group,and their photophysical properties were further explored.Electrical storage devices based on the same structure of small molecules,polymers and copolymers were prepared and the storage types these sandwich devices were investigated.Simultaneously,we designed and synthesized the Su FEx click reaction of the monomer of tert-butyldimethylsilyl ether at the 6-position of cyclodextrin and fluorosulfate(-OSO2F)monomer of 4,4'-dihydroxybenzophenone.The optimum conditions for the cyclodextrin polymer were obtained through a series of experiments.The effect of adsorption of metal ions on the spinning film of the ?-CD polymer was investigated.This research has broadened the path for the application of this new type of click chemistry in the preparation of functional polysulfates and provided a new method for the synthesis of cyclodextrin polymers.