Well-Designed Syntheses And Luminescent Properties Of Crystal Network Complexes Based On Flexible Bis(Pyridyl) Diamine

Crystal network complexes constructed from rigid and flexible bis?pyridyl?ligands have attracted intensive interests in recent decades owing to their novel topological structures and potential physical and chemical properties,in which researches on crystal network complexes constructed from flexible bis?pyridyl?ligands are less concerned.This is mainly because that the spacers of flexible bis?pyridyl?ligands have strong deformation abilities,which increases the difficulty of predicting network structures and performing properties.To date,the rational design of crystal network complexes and modulation of properties have not been performed.Therefore,according to the basic principle of crystal engineering and supramolecular chemistry,in this thesis,nine kinds of flexible bis?pyridyl?diamine ligands were synthesized by the reaction of pyridine carboxaldehyde,1,3-propanediamine or 1,2-ethylenediamine,in which the spacers present chelating coordination abilities and can be protonated step by step.With such characteristics,crystal network complexes with novel network structures or excellent fluorescence performances will be obtained.Accordingly,23 metal-organic or supramolecular crystal network complexes with silver?I?,copper?I?and H₂PO₄^-anion have been synthesized through self-assemble and hydro?solvo?thermal reaction,which were characterized by IR,TG,PL,powder and single-crystal X-ray diffraction.Silver?I?based complexes show?4,4?layer,helical chain,macrocyclic dinuclear,as well as 3D microporous structures.Copper?I?based complexes exhibit mononuclear,dinuclear,chain,layer and pcu network structures.Supramolecular complexs tuned by H₂PO₄^-anions exhibit 2-D or 3-D supramolecular networks.Moreover,silver?I?based complexes 1,2 and 5 show weak violet emissions,and copper?I?based complexes 11 and 13 exhibit strong yellow?MLCT?and blue?XLCT?emissions at 592 and 489 nm,respectively.Supramolecular crystal network complexes tuned by H₂PO₄^-anions show strong violet emissions at room temperature.