Research On The Design, Preparation And Identification Of Functional Compounds Containing Rigid N-organic Ligands

With the development of industrialization,problems such as energy storage and environmental pollution have become more and more serious.The design and synthesis of new porous framework materials with specific structures and functions is essential to solve the above problems.Among the many new materials,"porous materials"as an emerging material system have attracted the attention of scientists due to its unique pore structure and its special functions in the fields of machinery,adsorption,permeation,photoelectricity and biological activity.It has become the focus and hotspot of interdisciplinary research.MOFs have many advantages such as mild synthesis conditions,tailorable structures,and designable functions,which make them have potential application prospects in many fields such as gas storage and separation,ion detection,proton conduction,and adsorption of organic pollutants.Although MOFs materials have shown good properties in many fields,how to take full advantage of the"porosity"and"designability"of MOFs materials is still a very challenging thing.This also promotes the intersection of MOFs materials and other disciplines,and also opens up a new path for its development.Cucubit[n]uril has"hydrophobic cavities that can contain organic guest molecules,ions or small gas molecules","negatively charged ports capture metal ions or positively charged amine molecules through coordination and ion dipole interaction"and"positive The electrical outer wall absorbs organic aromatic molecules,ionic interactions and gas molecules through non-covalent bond action and ionic dipole action.It has become the focus of attention after continuing supramolecular chemistry to relay crown ethers,cyclodextrins,and calixarenes.A new type of cage-like supramolecular host molecule in,also makes the melon ring a"potential"organic building block.This thesis selects electron-deficient aromatic organic N-ligands,namely1,4-bis[2-(2-pyridyl)vinyl]-benzene(2-bpeb),1,4-bis[2-(3-Pyridyl)vinyl]-benzene(3-bpeb),1,4-bis[2-(4-pyridyl)vinyl]-benzene(4-bpeb)and 4-(4H-1,2,4-Triazol-4-yl)benzenesulfonic acid(HL)and other four ligands,we plan to investigate the formation of Q[8]-SOFs/MOFs with the cucubit[8]uril(Q[8])with a high degree of polymerization.Therefore,we first investigated the MOFs structure of the above ligands,and obtained 7functional complexes based on the above ligands.details as follows:(1)Complexes 1,2,and 3 are all based on 2-bpeb ligands,in which isostructural Zn-MOFs(1)and Cd-MOFs(2)three-dimensional framework complexes are obtained with the assistance of H2sdba.With the aid of H2PTA,three-dimensional framework complexes based on Co-MOFs were obtained(3).Property experiments show that:1 and 2 have high sensitivity and selectivity to Fe³⁺and Cr₂O₇^2-in the water phase,and 3 also shows high selective recognition of Fe³⁺,so 1-3 are expected to be used as chemical sensor materials.(2)Complex 4 is based on 3-bpeb ligand,which is bridged by H₂sdba to form seven-fold interspersed three-dimensional Zn-MOFs.Due to the presence of olefin bonds in the 3-bpeb ligand,in complex 4,the distance between adjacent olefins is very short,and the photochemical[2+2]polymerization reaction occurs under the induction of ultraviolet light,and complex 5 is obtained.5 can also be restored to 4 when heated.The experimental results of the properties show that:4 and 5 both selectively and sensitively exhibit the TNP sensing ability through the fluorescence quenching effect,and are expected to become TNP detection and identification materials.(3)Complexes 6 and 7 are based on the selection of4-(4H-1,2,4-triazol-4-yl)benzenesulfonic acid ligand,6 is a three-dimensional Cd-MOFs structure,and complex 7 is a simple complex.The experimental results show that the types of inorganic anions and metal ions affect the final structure of the complex.Complex 6 has good selective recognition of acetone molecules.Secondly,in this paper,three ligands of 2-bpeb,3-bpeb,and 4-bpeb were selected to interact with the common cucurbit[8]uril Q[8],and three cucurbit[8]uril-supramolecular self-assemblies were obtained,namely 8,9,10.The target type Q[8]-SOFs structure(8)was obtained by bpeb ligand,while Q[8]interacted with 2-bpeb to just form a simple host-guest compound:1:2 Q[8]@2-bpeb(9).when in the 4-bpeb-Q[8]system,only pure Q[8]-SOFs were obtained,indicating that organic molecules can promote the dispersion and arrangement of cucurbit[8]uril molecules.Property research shows that:8 exhibits strong fluorescence characteristics and can be identified and detected on Fe³⁺ions.