| Metal-organic framework materials?MOFs?have been widespread concerned by researchers,and are widely used in the fields of chemical sensing,gas separation and adsorption,catalyst,magnetism,optics,and so on due to their structures'regulability and loadability.However,on the one hand,the research on the generation mechanism of metal-organic frame materials is not very mature and cannot be accurately defined,and the theory requires a lot of experimental evidence.On the other hand,the structure of the material determines the nature of the material,and the nature of the material determines the application of the material.In order to develop materials with good performance,we must have new materials with unique structures as the basis for the research.All these factors require us to explore the synthesis of new functional complexes continuously.In this paper,thirteen novel coordination polymers with one-dimensional,two-dimensional and three-dimensional structures were synthesized through hydrothermal synthesis routes by using organic carboxylic acid as main ligands,such as 1,4-naphthalenedicarboxylicacid,3,5-pyrazoledicarbox-ylicacid,and3,5-pyridinedicarboxylic acid,coordinated assembly with transition metals and rare earth metals of Mn,Cu,Co,Zn,Er,Pr and introduing 1,2,4-triazole,1,10-phenanthroline monohydrate ligands as the auxiliary igands into the reaction system.The structures and compositions of the complexes were characterized by X-ray single crystal diffraction,thermogravimetric analysis,elemental analysis and infrared spectroscopy.The arrangement mode of cooperation unit in the complexes and the interaction between coordination units were further elucidated and analyzed by using the structural analysis software of Diamond,Olex and Topos.The magnetic and fluorescence properties of the complexes were investigated by variable temperature magnetic susceptibility and fluorescence emission/excitation spectra and the relationship between the structure and properties of the complexes was analyzed.These studies contents provide theoretical and methodological basis for the synthesis of novel complexes,providing abundant experimental data for the study of the generation mechanism of MOFs,and more possibilities for R&D of new materials with good performance.The specific findings of the works are summarized as follows:?1??A series of new transition metal complexes,{[Mn2(C12H6O4)2?C2H6OH??DMF??H2O?]·CH3OH}n?1?,{[Mn?III?(C12H6O4)?C2H5O?][Mn?II?(C12H6O4)?DMF??H2O?]}n?2?,{[Cu2(C13H9O4)4?H2O?2]}n?3?,{[Mn3(C12H6O4)4]2-(C11H18N4)2+}n?4?and{Mn3(C12H6O4)4}n?5?,were synthesized by using 1,4-naphthalenedicarboxylic acid as a ligand.Complexes 1,2 and 5 show a same 3D network structure via similar secondary structural units,but the central metal ion in the complex 2 occured the oxidation-reduction,forming a complex with mixed valence states.Complexes 3 and4 show a 3D structure relying on abundant hydrogen bonds.The temperature-dependent magnetic susceptibility measurements exhibit overall antiferromagnetic interactions between Mn-O-Mn bridged Mn?II?or Mn?II/III?centers for complexes 1,2 and 4,and a strong ferromagnetic interaction between the Cu?II?centers for complex 3 due to a weak interaction between two adjacent Cu?II?.?2??Four transition/rare earth metal ion complexes,{[Er2Zn?Hpdc?4?H2O?8]·2H2O}n?6?,{[Cu?C5H5O2N2?2?H2O?]·3H2O}n?7?,{Co?C7H3NO4??H2O?2}n?8?and{[CoNa2?C7H3NO4??H2O?3]2+·2?OH?-}n?9?were synthesized by using the N-heterocyclic dicarboxylate ligands as main ligands,for example,3,5-pyrazoledicar-boxylic acid,and the solvent water molecules as auxiliary ligands.Complex 6 shows a 3D heterometallic framework with nested sandwich-type structure,built by single-ionic structural units and diversified hydrogen bonds.Complexes 7 and 8 show a 3D supramolecular structure via abundant hydrogen bonds.The structure of the heteronuclear complex 9 is an anti-parallel 1D chain structure formed by the interconnection between ligands.The solid-state luminescent property investigation shows that emission lifetime span of the complex 6 was at the microsecond level in the visible region,which is classified as a phosphorescent material.The temperature-dependent magnetic study suggest that the complexes 7 and 8 exhibit overall antiferromagnetic interactions.?3??The polycarboxyl ligands and transition/rare earth metal ion complexes,{[Mn2?C8H6O8??H2O?5]·2H2O}n?10?,{Pr?Hbtec??H2O?}n?11?,{Cu5?btec?2?1,2,4-trz?2?H2O?2??-OH?2}?12?and{Cu2?phen?2?Cl?2}n?13?,were further synthesized by using 1,2,3,4-butanetetracarboxylic acid,1,2,4,5-benzenetetracarboxylic acid as carboxyl ligands,and 1,2,4-triazole,1,10-phenanthroline monohydrate as N-heterocyclic dicarboxylate ligands.Both complexes 11 and 12 are 3D supramolecular structures directly connected to the central metal ion via the carboxyl ligand,while the complexes 10 and 13 are two-dimensional structures.The difference in the structure of complexes 10 and 13 is that the 2D network of the complex 13 is formed by hydrogen bonds. |
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