| In the past dacades,metal-organic coordination crystalline material has characteristics of porosity,functional tunability,high specific area,and has the common features of both organic and inorganic materials,giving it rich physicochemical properties.metal-organic coordination crystalline material has been widely used in gas adsorption,fluorescence sensing,organic catalysis,photoelectrocatalysis,energy storage,drug delivery.From the point view of crystal engineering,the choice and design of organic components play an important role in the design of such materials and their function exploration.At present,organic components used for assembling crystalline materials include carboxylic acids,azaheterocycles,Schiff bases,polyketones,polyamines,and the like.Among them,trimesic acid,terephthalic acid,terpyridine and 4,4'-dipyridyl are commonly used as star organic components.Many well-known metal-organic coordination crystalline material have been constructed,such as MOF-5?HKUST-1?MIL-100?UiO-66?MOF-500?MIL-143 and so on.Therefore,the design and synthesis of new organic components are still attracting a lot of researchers in this field.Based on the works we have done in our group,our research mainly focuses on the design and performence exploration of transition-rare earth heterometallic crystalline materials.We have,therefore,investigated a newly designed polytopic ligand with three pyridyl donors and three carboxylic group,namely 4-(2,4,6-tricarboxylphenyl)-2,2':6',2"?terpyridine(H3L),in the synthesis of novel crystalline materials.H3L has been selected to construct novel crystalline materials according to the following reasons:(a)H3L is a bifunctional bridging ligand with N,O donor which will form many structures with different conformations or versatile coordination modes by linking different metallic ions through coordination bonds.(b)H3L has a large ?-conjugated linear structure that helps to form a good connection between the donor and acceptor to fulfill electron transport.By the same token,H3L have been employed as an organic building block to design novel crystalline materials.Their synthetic methods,structural characteristics,electrocatalysis,magnetic and fluorescence,and their sensing performance were explored.In the first chapter,we described the structures and related applications of polyacid and terpyridyl based crystalline materials,respectively.In the second chapter,The molecular formula of complex 1-4 are shown below:{[Co(H2L)2]·5H2O}n(1){[Cu(HL)]·2H2O}n(2){[Ag(H2L)]·H2O}n(3){[Zn2(HL)2]·H2O}n(4)? complex 1 is a 0D crystalline material,terpyridyl moieties from two the ligands coordinate with one Co2+in the tridentate-chelating fashion and the carboxylate groups are free.Part of the carboxylate groups are deprotonated to balance the charge in the system.? Complex 2 is a Cu-based one-dimensional crystalline material.Terpyridyl in HL2-are coordinated with Cu2+ions in the tridentate-chelating fashion.One carboxyl groups are coordinated with Cu2+ions in a monodentate bridging fashion to form a[Cu2L2]unit.Through the coordination of Cu2+and carboxyl groups,every two one-dimensional single chains are arranged in opposite directions to form the final one-dimensional ladder chain.there also exsit ?-? interactions and hydrogen bonds in the system and finally leading to a 3D supermolecule structure.? In complex 3,the terpyridine moiety of the organic ligand is coordinated with the Ag+ion in the same fashion,here only one carboxyl group is deprotonated and coordinated with Ag+ion.The organic ligands are connected end to end by Ag+ions to form a one-dimensional chain.The existence of ?-? interactions and hydrogen bonds between adjacent ligands provides favorable conditions for the formation of 3D supermolecule structure.? Complex 4 is a Zn-based 2D crystalline material,and the pyridyl group in the organic ligand binds with Zn2+in the same tridentate-chelating fashion.Two carboxyl groups are deprotonated to participate in coordination to generate a 2D net.There are complex hydrogen bonds and ?-? interactions in the system,forming a 3D structure.By selecting different metal ions and organic ligands to react under different conditions,different transition metal-based crystalline materials are constructed.Due to the difference in the deprotonation of the tricarboxylic acid moiety and the nature of the metal ions themselves,The structure of the complex 1,2,3 and 4 shows a big difference.At the same time,the physicochemical properties of complex 1,2,3 and 4,such as PXRD,TG and solid fluorescence were tested.In the third chapter,four isomorphic Ln-based crystalline material were obtained,{[LnL(H2O)]·H2O}n(Ln3+=Sm3+,Eu3+,Tb3+,Dy3+)(5)The structure of Tb-based crystalline material was used as an example to explore their structure.The pyridyl group in the organic ligand binds with Tb3+in tridentate-chelating fashion in complex 5 to form a 2D layer.Different from complex 4,the topological network of the complex 5 is closer to the parallelogram;the two-dimensional layers are stacked in the ABAB...manner,and the final three-dimensional structure is formed by hydrogen bonding and ?-? interaction between the layers.PXRD,FT-IR,thermal behavouir and solid fluorescence of complex 5-Sm?Eu?Tb?Dy were checked.In the fourth chapter,12 heterometal-based crystalline materials were obtainted.{[Ln Co(L)(HL)(H2O)3]·3H2O}n(Ln3+=Sm3+,Eu3+,Tb3+,Dy3+)(6){[LnCu(L)(NO3)2(H2O)]}n(Ln3+=Sm3+,Eu3+,Tb3+,Dy3+)(7){[(CH3)2NH2][LnZn3(L)3(HCOO)(H2O)2]·5H2O}n(Ln3+=Sm3+,Eu3+,Tb3+,Dy3+)(8)?6 is a series of isomorphic Co/Ln two-dimensional heterometal-based crystalline materials.In the Co/Ln heterometal-based crystalline materials,there are two coordination modes for the carboxylic group in the ligand,and one that Only two protons are removed,(HL2-),and the other that all the protons are totally removed,(L3-).Two such organic ligands are coordinated with Co2+ions to form a Co(HL)(L)unit.Different Co(HL)(L)units are linked by Tb3+to form a one-dimensional helical structure.The helical chain is again connected by Tb3+ions to form a two-dimensional layer.Also,as a two-dimensional material,unlike complex 4 and 5,the topological network of complex 9 is close to a hexagon.Different two-dimensional layers form hydrogen bonds with free water molecules in the arrangement of ABAB...to form the final three-dimensional structure.? 7 is a series of isomorphic three-dimensional Cu/Ln heterometal-based crystalline materials.Taking a 7-Tb heterometal-based crystalline materials as an example,one Cu2+and one Tb3+form a[TbCu(COO)2(NO3)2]heterometal cluster unit.The completely deprotonated ligands link different[TbCu(COO)2(NO3)2]heterometal cluster units,further expanding into a three-dimensional structure.Topological analysis shows that both[TbCu(COO)2(NO3)2 heterometal cluster units and organic ligands can be regarded as 4-connected nodes,and the entire structure can be consideed as a 4-connected node network topological symbol(44.62).?8 is a series of isomorphic three-dimensional Zn/Ln heterometal-based crystalline materials,and the structural characteristics of the 8-Tb heterometal-based crystalline materials are analyzed.The terpyridine moiety of the organic ligand is coordinated with Zn2+in a tridentate-chelating coordination mode.The completely deprotonated carboxylic acid groups are coordinated with Tb3+through different coordination modes.The ratio of Tb3+to Zn2+in the complex 8-Tb is 1:3.The highest possible symmetry of 3D network is P63/mmc and helical structures are also observed in 8-Tb.and heterometal-based crystalline material can be condsider as two nodes(4,6)-tcj network with the point symbol of(44.62)(48.66.8).PXRD?TG?FT-IR and solid fluorescence of 8-Tb,8-Eu,11-Dy were checked.In the fifth chapter,? complex 3,4,5-Tb,and 5-Eu exhibit excellent fluorescence sensing performance for Fe3+ cation and Cr2O72-anion.Complex 3 as a sensor to Fe3+cations with a KSV of 0.47 ppm-1 and LOD of 0.073 ppm;Complex 3 as a sensor to Cr2O72anion with a KSV of 0.37ppm-1 and LOD of 0.084ppm.Complex 4 as a sensor to Fe3+ cations with a KSV of 0.0712ppm-1 and LOD of 0.44ppm;Complex 4 as a sensor to Cr2O72-anion with a KSV of 0.0507ppm-1 and LOD of 0.63ppm.Complex 5-Tb as a sensor to Fe3+cations with a KSV of 6.01 ×104M-1 and LOD of 0.5?M;Complex 5-Tb as a sensor to Cr2O72-anion with a KSV of 7.35×104M-1 and LOD of 0.41?M.Complex 5-Eu as a sensor to Fe3+cations with a KSV of 3.8×104M-1 and LOD of 0.79?M;Complex 5-Eu as a sensor to Cr2O72-anion with a KSV of 6.35×104M-1 and LOD of0.47?M.5-Tb show the best performance.? For different nitro compounds,the fluorescence intensity of complex 4 has been quenched to varying degrees,with the highest quenching efficiency for 2,4-dinitrophenol(2,4-DNp).Complex 4 as a sensor to 2,4-DNP with a KSV of 9.1×104 M-1 and LOD of 0.33?M.Both Complex 4 and 5-Tb are excellent sensors to acetone.5-Eu has best performance.? In the exploration of the sensing performance of antibiotics,complex 4 and 8-Tb were found to be a sensor to NFs(furazolidone,FZD,nitrofurazone,NFZ,nitrofurantoin,NFT).Complex 4 as a sensor to NFT,NFZ and FZD with KSV of 2.88×105 M-1,2.28×105 M-1,5.28×105 M-1,respectively and LOD of 0.104?M,0.175?M,0.056?M,respectively;Complex 8-Tb as a sensor to NFT,NFZ and FZD with KSV of 9.25 × 105M-1,1.83×106M-1,1.151×106M-1,repectively and LOD of 0.018?M,0.002?M,0.003?M,respectively;Complex 5-Tb as a sensor to RDZ with a KSV of 9.98×104 M-1 and LOD of 0.3?M.? the reason why the solid fluorescence was quenched was summarized by checking the behavior of sensing antibiotics.In the fifth chapter,? complex 1 and 2 show excellent electrocatalytic hydrogen evolution properties.For complex 1 and 2,values of ?10 reach 375mV and 231mV,Tafel slopes reach 97mV dec-1 and 129mV dec-1,respectively.By exploring the HER performance of 6 and 7,6-Sm and 7-Sm have the best electrocatalytic performance.The values of ?10 reach 436mV and 401 mV for 6-Sm and 7-Sm,respectively.The values of Tafel slope are 147mV dec-1 and 143mV dec-1 for 6-Sm and 7-Sm,respectively.6-Sm and 7-Sm also have smaller impedance and larger active surface.6-Tb,6-Eu,6-Sm,and 6-Dy all showed antiferromagnetic properties. |
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