Preparation And Stimulus Response Performance Of Eu³⁺-containing Metallopolymer Based On Phenanthrenequinones

Stimulus-response materials,as a new type of intelligent materials,have been recently attracting wide attention,especially their requirements of visualization and ultra-high sensitivity for acid-base stimulation and sensor of metal ion are highly appreciated.Herein,two new phenanthrenequinone-type while vinyl-modified organic molecules of N-VB-PIandVB-OH-PIweresynthesizedN-VB-PI=N-（4-（1-（4-vinylbenzyl）-1H-phenanthro[9,10-d]imidazol-2-yl）phenyl）-N-phenylbenzenamine;VB-OH-PI=（4-styrene）-2-（1H-phenanthro[9,10-d]imidazol-2-yl）phenol),respectively.Their photo-physical properties show that N-VB-PI exhibits fluorescent change from blue,to white,and to yellow-green with different acidity conditions in solution;as to VB-OH-PI,it displays the selective sensing to Zn²⁺ion as compared to other metal ions.Secondly,based on the self-assembly of theb-diketone ligand HBTFA（4,4,4-trifluoro-1-phenylbutane-1,3-dione）,theancillaryligand4-vp-2,2’-Bpyand LnCl₃.6H₂O（Ln=La,Eu,Tb or Gd）,the series of styryl-functionalized complexes[Ln（BTFA）₃（4-vp-2,2’-Bpy）]（Ln=La,1;Ln=Eu,2;Ln=Tb,3;Ln=Gd,4）were obtained,respectively.Further besides the characterization of elemental analysis（EA）,Fourier transform infrared spectroscopy（FT-IR）and electrospray ionization mass spectrometry（MS）,nuclear magnetic resonance hydrogen spectrum（¹H NMR）and X-ray single crystal diffraction（XRD）,their photo-physical properties were also examined.Finally,using the styryl-modified organic N-VB-PI and the vinyl-modified lanthanide complexes[Ln（BTFA）₃（4-vp-2-2’-Bpy）]（Ln=La,1;Eu,2）as the copolymerized monomers,their copolymerization with NVK in the presence of AIBN（2,2-Azobisisobutyronitrile）were carried out to obtain the series of PVK-supported and Ln³⁺-containing metallopolymer-type hybrid materials Poly(NVK-co-[（N-VB-PI）]-co-[Ln（BFTA）₃（4-vp-2-2’-Bpy）]（Ln=La,1;Ln=Eu,2）,respectively.Moreover,their characterization was founded from FT-IR,¹H NMR,X-ray powder diffraction（PXRD）and gel permeation chromatography（GPC）.Meanwhile,in dependence of the feeding ratio and excitation wavelength,the color-tunable to direct white-light was realized for Poly（NVK-co-[（N-VB-PI）]-co-2）.More importantly,its reversible and fast acid-base stimulation effect and application for NUV-WLED device were also explored.