| In this paper,different polyaromatic carboxylic acid ligands and transition/rare earth metals ions were selected to construct four series of 25 coordination polymers with stable structure and excellent performance by water/solvothermal method,and the factors affecting the synthesis of coordination polymers,including temperature,solvent,pH value and material molar ratio were summarized.The structure and physicochemical properties of coordination polymers were studied by X-ray single crystal diffraction,X-ray powder diffraction,IR spectra,elemental analysis,spectrum analysis,thermogravimetry analysis and magnetic analysis,et al.The main contents are as follows:1.Based on 2-?3?,4?-dicarboxylphenoxy?isophthalic acid?H4dpc?,4,4?-bis?imidazolyl?biphenyl?bibp?ligands and rare earth metals,nine rare earth metal organic coordination polymers were synthesized by hydrothermal method: {[Ln?dpc??2H2O?]·?bibp?0.5}n?La?1?? Ce?2?? Pr?3?? Nd?4?? Sm?5?? Eu?6??;{[Ln?dpc??bibp??H2O?]·?H2O?}n?Tm?7??Yb?8??Er?9??.X-ray single-crystal diffraction demonstrates that 1-6 are isomorphous and isostructural.One layer of uncoordinated bibp?type B?ligands are sandwiched between two adjoining 2D layers?type A?connected by the dpc4-ligands.Both types of layers are further interlinked alternately in?···A-B-A-B···?n style to give rise to a 3D supramolecular framework through hydrogen bond interactions.7-9 are isomorphous and isostructural,the 2D structure formed by dpc4-ligands and bibp ligands were connected to each other by hydrogen bond interactions to a 3D supramolecular framework.Most notably,luminescent and sensing properties of 6 were performed,indicating that 6 behaves a multi-responsive luminescent sensor toward Fe3+,Cu2+,Cr2O72-,nitrobenzene?NB?,and Tryptophan?Try?with high sensitivity,selectivity,stability,recyclability,and anti-interference ability against the corresponding coexistence of other ions or molecules based on high luminescence quenching efficiency.Furthermore,the possible luminescent sensing mechanisms for the above analytes have also been discussed in detail,which are supported by PXRD analysis,inductively coupled plasma-atomic emission spectrometer?ICP-AES?,UV-vis spectra and X-ray photoelectron spectroscopy?XPS?and the density functional theory?DFT?.2.Based on 1-?3-carboxylbenzyl?benzimidazole-5,6-dicarboxylic acid?H3caba?,4,4'-bipyridine?bipy?,4,4?-bis?imidazolyl?biphenyl?bibp?ligands and transition/rare earth metals ions,five coordination polymers were synthesized by solvothermal method: [Zn3?caba?2?H2O?2]n?10?,[Co?caba??bibp?1.5?H2O?]n?11?,{[Dy4?caba?4?H2O?8]·?H2O?5}n?12?,{[Tb4?caba?4?H2O?8]·?H2O?5}n?13?,{[Er2?caba?2?H2O?4]·?H2O?2}n?14?.Structural analysis shows that coordination polymer 10 exhibits a 3D architecture through covalent bonds of caba3-ligands;the structure of coordination polymer 11 is bridged by caba3-ligands and bibp ligands to form a 2D grid,and 3D structure is formed by two kinds of hydrogen bonds;X-ray single-crystal diffraction demonstrates that 12-14 are isomorphous and isostructural,the 3D network were connected by 2D layered structure via four types hydrogen bonds.The remarkable character is that coordination polymer 10 and 12 demonstrates highly selective and sensitive recognition for Fe3+,coordination polymer 13 has dual recognition for Fe3+ and Tryptophan?Trp?,and coordination polymer 11 exhibit antiferromagnetic behaviors.The quenching mechanism were explored by PXRD,UV-Vis,XPS and other methods.3.Based on 2,4,4',6-biphenyltetracarboxylic acid?H4bptb?,4,4'-bis?imidazolyl?biphenyls?bibp?and 4,4'-bipyridine?bipy?ligands and transition metals,five coordination polymers were synthesized by solvothermal method: {[Co?bptb?0.5?bibp??H2O?2]·H2O}n?15?,[Mn4?bptb?2?bibp?3?H2O?4]n?16?,{[Ni?bptb?0.5?bibp??H2O?2]·H2O}n?17?,[Ni2?bptb??bipy?2?H2O?3]n?18?,[Cd3?bptb?2?bibp?3?H2O?4]n?19?.X-ray single-crystal diffraction demonstrates that coordination polymer 15 and 17 are isomorphous and isostructural,the 1D "bamboo ladder" chain connected by the bibp and bptb4-ligands to form a 3D structure via hydrogen bond and ?···? interactions;the structure of coordination polymers 16,18 and 19 exhibits 3D architecture through covalent bonds of ligand.Coordination polymer 17 and 18 exhibit antiferromagnetic behaviors;coordination polymers 16,17 and 18 have good electrochemical properties and coordination polymer 19 exhibits good fluorescence quenching response to Fe3+,Cr2O72-and Cr O42-.4.Based on 2,4,6-tris?4-carboxyphenyl?-1,3,5-triazine?H3tpta?,1,4-bis?1-imidazole?benzene?bib?,2,2?-bis?4-carboxyphenyl?-6,6?-?1-h-benzimidazole??H2bipb?,1,3,5-tris?4-?imidazolyl?phenyl?benzene?tipb?ligands and transition metals,six coordination polymers were synthesized by solvothermal method: {[Co?tpta??bib??H2O?]·DMF}n?20?,{[Ni?tpta??bib??H2O?]·DMA}n?21?,[Cu?tpta??bib?0.5?H2O?]n?22?,{[Zn?tpta?2?bib?4]·?H2O?3}n?23?,{[Cd?tpta??bib??H2O?]·DMF·H2O}n?24?,{[Co4?bipb?2?tipb?4?H2O?2]·?H2O?6}n?25?.X-ray single-crystal diffraction demonstrates that coordination polymer 20?21 and 24 are isomorphous and isostructural,which are bridged by tpta3-and bib ligands to form a 2D grid connected by two kinds of ?···? interaction to form 3D structure;the structure of coordination polymer 22 is a 2D grid formed by bridging of tpta3-and bib ligands,and 3D structure is formed by ?···? interaction connection;coordination polymer 23 is a 3D grid formed by connecting tpta3-and bib ligands,and a higher-level structure is formed by ?···? weak interaction connection.Coordination polymer 20 exhibits antiferromagnetic behaviors;coordination polymers 21 have good electrochemical properties and coordination polymer 23 exhibits good fluorescence quenching response to Fe3+,Cr2O72-and Arginine?Arg?. |
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