Syntheses,Regulation And Properties Of Heterometallic Porphyrin-Based Coordination Frameworks

Metal-organic frameworks?MOFs?are a family of microporous crystalline materials that have potential applications in adsorption,separation,catalysis,and sensing.Compared to single-component physical mixing,multi-component MOFs own chemical tailorability and spatial control of functional groups at the molecular scale,and also provide better function and property.As a branch of multi-component MOFs,heterometallic MOFs have different metals which are usually in equivalent crystallographic positions,so it is difficult to distinguish them,to get a MOF that contains two or more metal types coexisting and evenly arranging.At present,more researches have been focusing on bimetallic MOFs,and the selected metals must have great differences in coordination affinity and geometry.For example,the combination of a nitrogen-philic transition metal and an oxophilic rare earth metal can lead to heterometallic 3d-4f MOFs.It is very difficult to build a MOF containing three or more metal types or even of the same coordination configuration.We choose 5,10,15,20-tetrakis?4-pyridyl?porphyrin?TPyP?as the ligand and first metalize it into M_A-TPyP?M_A can be iron,cobalt,nickel,copper,zinc,palladium,etc.?,coupled with high-valent metal perfluorinated salt(M_B-F_6-xO_x-M_C,M_B can be silicon,germanium,bismuth,molybdenum,tungsten,etc.,M_C can be iron,cobalt,nickel,copper,zinc,cadmium,etc.)to fabricate serial coordination framewroks,abbreviated as M_A-M_B-M_C,of which the square layer M_A-TPyP-M_C was supported by the pillar[(M_B-F_6-xO_x)^y-].The purpose of this paper is to synthesize heterotrimetallic MOFs based on pyridylporphyrin-perfluorous pillar,namely M_A-M_B-M_C,and to explore the influence of different metal combinations on the performance of M_A-M_B-M_C.?1?The metal porphyrin-copper hydrofluoric acid copper complex,namely M_A-Nb-Cu?M_A is iron,nickel,zinc?,has very good thermal and chemical stability and a uniform distribution of the electrostatic field,forming a moderate affinity with CO₂,it can be used as a catalyst to fix CO₂ and combine it with epoxy ether derivatives to form electrolyte carbonates,which is highly efficient and complete.?2?Benzene series is a kind of substance that will harm the environment and human health.It is of great significance for its identification and identification.Zinc porphyrin zinc tungstate fluoride hybrid material,namely Zn-W-Zn,has a fluorescence response to the benzene series.The fluorescence intensity depends on the structure type of the benzene series,and the presence of water quenches the fluorescence.In addition,we synthesized a cubic structure of lanthanide MOFs containing a zinc aqueous complex as a guest molecule,namely Ln-pdc-Zn?pdc is pyrazole-3,5-dicarboxylic acid,Ln is lanthanum,cerium,lanthanum,gadolinium?.This kind of material has good chemical stability,especially superhydrothermal stability,and there is a rich hydrogen bond network.The proton conductivity of the material exceeds10^-3 S cm^-1 at 97%relative humidity and 25?.