Synthesis And Properties Of Functional Materials Based On Metal Complexes And Nitrogenous Organic Compounds

Organic-inorganic hybrid metal complexes take the inorganics as the rigid base and the intermolecular hydrogen bond interaction force as the connection,combining with the structural diversity of organics,spatial flexibility and high molecular polarizability and other characteristics,which can be widely used in the fields of electricity,optics,magnetism,heat and catalysis.The stimulation-responsive crystalline materials of organic-inorganic hybrid metal halide complexes were obtained by regulating the types of halogen atoms and small organic molecules and introducing metal halides and nitrogen-containing organics into the solid space structure.This kind of materials have broad application prospects in high-tech fields such as storage devices,piezoelectric sensors,flexible wearable devices and photoelectric transformation.In this paper,selecting cobalt,molybdenum,manganese and other halogen-metal ion complexes as stereoscopic building blocks,with pyridine,aniline and DABCO and other nitrogen-containing organics respectively,eight kinds of halogen metal complexes and nitrogen-containing organic hybrid multifunctional materials that have not been reported were obtained in methanol,ethanol,water and other mixed solvent evaporation:[(C₅H₈N₂)²⁺][(Co Cl₄)^2-](1)?[(C₅H₇N₂)₂⁺][(Co Cl₄)^2-](2)?[(C₆H₉N₂)₂⁺][(Mo O₂Cl₃(H₂O))^-][Cl^-](3)?[(C₇H₁₁N₂)₂⁺][(Mo OBr₄(H₂O))^-][Br^-](4)?[(H₂DABCO)²⁺][(Mo O₂Cl₃(H₂O))^-][Cl^-](5)?[(C₆H₈N)₂⁺][(Mo O₂Cl₄)^2-](6)?[(HDMAP)₂⁺][(Mn Cl₄)^2-](7)?[(C₇H₁₁N₂)₂⁺][(Mn Cl₄)^2-](8),and their structure and properties were characterized and analyzed by infrared spectroscopy,X-ray single crystal diffraction,thermogravimetric analysis and XRD powder diffraction,dielectric constant,solid-state fluorescent and ferroelectric tests.Compounds 1 and 2 were embedded into the three-dimensional framework of[Co Cl₄]^2-with disordered aminopyridine molecules as building blocks,resulting in the crystalline materials to produce dielectric anomaly near 200 K at the same time.Compound 2 produces a reversible phase transition and ferroelectric properties,displaying that 1 and 2 belong to new dielectric switch functional materials and ferroelectric phase transition functional materials,respectively.Compound 3-6 takes[Mo O_pL_qH_f]^n-as the anion building blocks,and interacts with cations through hydrogen bondings to form one-dimensional chain and multi-dimensional network structure in space.Reversible dielectric anomalies in the range 160 K to 238 K were observed in the four compounds due to the deformation of net structure.Among them,compound 3 belongs to a new type of dielectric switch functional material.Compound 4 is a reversible phase transition-dielectric coupling functional material.Compounds 5-6 showed perfect ferroelectric properties.Their saturation polarization values of P_Sare 0.065?C/cm²and 0.432?C/cm²respectively,which belong to the new ferroelectric functional materials.Compound 7-8 takes[Mn Cl₄]^2-as the anion building blocks,and their internal structural framework with manganese atoms as the vertex deforms with the change of temperature,resulting in the dielectric anomaly of two compound at 230 K in the heating process.The photoluminescence properties are induced by the energy level transitions(e_g)²(t_2g)³and(e_g)¹(t_2g)⁴in the valence electron layer of manganese ions.Compound 7-8 belongs to photoluminescence and dielectric anomaly functional materials.