Study On The Construction And Properties Of Metal Phosphor/phosphonate Guided By Photochromic And Photomagnetic Coupling

Inorganic–organic hybrid photochromic materials exhibit attractive application prospects in molecular switching,detection,biology,and molecular machines due to the unique property between each component.This paper aims to synthesize functional complexes with photochromism and photomagnetism.A series of hybrid materials with photochromic/photomagnetic properties are synthesized via introducing a2,4,6-tris?4–pyridyl?-1,3,5-triazine?TPT?ligand into the metal–phosphorus/phosphonate system,and their structures and properties are characterized.The main results are summarized as follows:Firstly,,a new complex[Zn₃?H–HEDP?₂?TPT?₂?H₂O?]·?H₂O??1?with reversible photochromic properties is synthesized through introduced TPT to the metal–phosphine?1–hydroxyethylidene diphosphonic acid,H₄–HEDP?system by hydrothermal reaction.The Zn–HEDP layer acts as an electron–donor?ED?with the TPT ligand as an electron–acceptor?EA?,the 3D pillar–layer structure is constructed with an ordered arrangement of[–ED–EA–ED–EA–].From X-ray to visible light,the complex exhibits obvious light responses,with the coloration time of 0.1 s when exposed to UV light.In addition,the purple samples can remain stable at ambient temperatures for over 3months.Secondly,two isomorphous metal–phosphates M?H₂PO₄??C₂O₄?_0.5?TPT?_0.5·H₂O?M=Zn,2;M=Mn,3?with pillar–layer structures are synthesized by solvent–free synthesis method via replacing the phosphine with the phosphorus,.Both complexes show photochromic properties.The room temperature magnetic susceptibility of complex 3decreases by 16.2%after irradiation,exhibiting an obvious photodemagnetization effect.Thirdly,on the basis of the previous work,a 1D Dy^IIIII chain[Dy₃?H–HEDP?₃?H₂–HEDP?₃]?H₃–TPT?₂?H₄–HEDP??H₂O?₁₀?4?is synthesized via replacing the transition metal with an anisotropic rare–earth metal Dy³⁺.The complex exhibits not only photochromic behavior but also strong exchange couplings between Dy ^IIIII ions and photogenerated radicals.Remarkable slow magnetic relaxations is observed at low temperatures,showing the single molecule magnetic behavior.