| Aliphatic cyclo-o-dicarboxylic acid is a kind of flexible ligand.They can construct metal-organic framework which has novel structure and excellent performance with the metal ions.We designed and explored a series of MOFs based on the aliphatic cyclo-o-dicarboxylic ligands by controlling the reaction conditions.The research has the following four parts:1.Synthesis,Structure and Properties of MOFs based on clip-like 1,2-cyclo propanedicarboxylic acid LigandThere are six MOFs[Ln2?ccpd?3?H2O?3]n?Ln=Eu?1?;Tb?2?;Dy?3??,[La9??4-dcd?12??3-O?2?H?]n?4?,[Gd2??3-OH?2??3-dcd???2-ac?2?H2O?]n?5?and[Cd??4-dcd???2-H2O?]n?6??ac=acetate?have been synthesized by cis-1,2-cyclopropanedicarboxylic acid?H2ccpd?,cis-3,3dimethylcyclopropane-1,2-dicarboxylic acid?H2dcd?and metals ions under hydrothermal conditions.From the performance test,we are able to know that 1 and 2 show better photoluminescence properties.4 represents the first report of the 3D Ln-CPs based on nonanuclear lanthanide clusters,although it shows extremely low gas uptakes.5 characterizes a novel one-dimensional ladder-like chain[Gd4?OH?4]n decorated with mixed ligand ribbons.Gd···Gd distance in 5 induces the antiferromagnetic interactions between adjacent Gd3+cations within the hydroxyl-bridged binuclear unit.2.Synthesis,Structure and Properties of double ligands MOFs base on clip-like1,2-cyclopropanedicarboxylic acidWe synthesized six mixed components MOFs,Ln?ccpd??bzc??H2O?]n?Ln=Eu?7?;Tb?8?;Dy?9??,[Zn?dcd??bipy?0.5]n?10?,[Co?dcd??bipy?0.5]n?11?and[Cu?bipy?2?H2O?1.5?Hdcd?2·?H2O?3.5]4n?12?,based on strategy of double ligands Which is cis-1,2-cyclopropanedicarboxylic acid?H2ccpd?and cis-3,3 dimethylcyclopropane-1,2-dicarboxylic acid?H2dcd?as the main organic ligands,adding benzoic acid?bzc?and 4,4?-bipyridine?bipy?as the second ligand.The single-crystal data shows that 7-9 and 10-12 are 1D chain structures and 2D layer structures,respectively.In addition,7-9 has good photoluminescence properties.Comparing with 1-3,we can determine that luminescence properties enhance by adding the second ligand.Furthermore,10 displays fluorescent emission assigned to the intra-ligand fluorescence emission.Both 11 and 12 exhibit antiferromagnetic coupling interactions.The carboxylate bridges existed in?3-dcd ligands can effectively mediate the antiferromagnetic interaction between Co2+ions in 11,whereas strong hydrogen bonds are effective magnetic exchange pathways in 12.3.Synthesis,Structure and Photoluminescence Properties of Ln-MOFs based on saddle-like 1,2,3,4-cyclobutane tetracarboxylate ligandA new family of three-dimensional lanthanide MOFs based on saddle-like 1,2,3,4-cyclo-butane tetracarboxylate ligand,formulated as[Nd??6-Hcbtc??H2O?]n?13?,[Tb??6-Hcbtc??H2O?]n?14?,[Tm2??6-cbtc???8-cbtc?0.5?H2O?]n?15?and[Yb2??6-cbtc???8-cbtc?0.5?H2 O?]n?16?,have been assembled from the ligand H4cbtc which is derived from the in-situ hydrolysis reaction of cyclobutane-1,2,3,4-tetracarboxylic dianhydride and lanthanide ions.Furthermore the complex 14 has good luminescent properties.4.Synthesis,Structure and Photoluminescence Properties of Ln-Na Bimetallic Metal-Organic Frameworks base on saddle-like 1,2,3,4-cyclobutane tetracarboxylic ligandOn the basis of the complexes 13-16,by adding deprotonating reagent?NaOH?and1,3-propanediamine-N,N,N,N-tetraacetic acid?PDTA?,the original 3D Ln-Na bimetallic metal-organic frameworks based on H4cbtc have been successfully constructed,Which is[PrNa??9-cbtc??H2O?]n?17?,[EuNa??9-cbtc??H2O?]n?18?,[TbNa??9-cbtc??H2O?]n?19?and[ErNa??6-cbtc???2-H2O??H2O?2?H2O?]n?20?.Analysising the Fluorescent data,we arrive at a conclusion that 18 and 19 have better luminescence properties and introducing the second metal enhances the luminescence properties. |
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