Preparation And Properties Of Solid-state Fluorescent Materials For Metal Complexes

Solid-state fluorescent materials for metal complexes have been widely applied in dye lasers,organic light emitting diodes?OLEDs?,data recording and storage,and security printing.With the development of science and social progress and with a stimulating response,solid fluorescent materials have become the focus of attention.Such materials can respond to external conditions by changing conditions such as mechanical grinding?force-induced discoloration?,heat treatment?thermochromic?,light treatment?photochromic?,energization?electrochromic?and by vapor fumigation stimulus to show different light properties.This kind of sensitive material has important practical significance and wide application prospect in information recording,data storage,anti-counterfeiting trademark and optoelectronic device.Naphthalimide Schiff bases,benzimidazoles and benzoxazoles derivatives have become the focus of attention because of their good coordination ability and structure diversity.The complexes synthesized from these derivatives are not only structurally easy to modify and have different coordination modes,but also have good luminescent properties.Based on the above research background,a series of novel complexes were designed and synthesized by using naphthalimide Schiff bases,benzimidazolylpyridine and benzoxazolylpyridine as ligands.The compounds were characterized by IR,NMR and X-ray diffraction.The solid-state fluorescence properties and thermal stability of the complex were studied.The details are as follows:1. Introduce the related concepts of solid-state fluorescent materials for metal complexes.2.?HL¹ and HL²?were synthesized from 1,8-naphthalene anhydride as raw materials.?HL¹=N-n-butyl-4-[?E?-2-???2-aminoethyl?imino?methyl?phenol]-1,8-naphthalimide and HL²=N-n-butyl-4-[?E?-2-???2-aminoethyl?imino?methyl?-6-methoxyphenol]-1,8-naphthalimide? and synthesizing three novel complexes:[Cu?L¹?₂]?1?,[Zn?L¹?₂?Py?]₂·H₂O?2?,[Ni?L²?₂?DMF?₂]?3?were characterized.Then,the stability,solid-state fluorescence properties and bio-related properties were studied.The results of fluorescence experiments show that complex 2 has obvious yellow-green fluorescence,which is attributed to the metal ion perturbation of the ligand luminescence.Compared with ligand HL¹,complex quenching of complexes 1 and 3 occurs.3.2-?3'-pyridyl?-benzoxazole?3-PBO?and 2-?4'-pyridyl?-benzoxazole?4-PBO?were synthesized by using 2-aminophenol,3-picolinic acid and 4-picolinic acid as starting materials.Three complexes[Cd?3-PBO?₂?NO₃?₂?H₂O?₂]CH₃CN?4?,[Zn?4-PBO?₂?NO₃?₂]?5?and[Ag?4-PBO?₂pic]_n?pic=picric acid??6?were synthesized and synthesized.The stability,solid-state fluorescence properties,and electrochemical properties were studied.The solid-state fluorescence spectra of the metal complexes showed that the complexes 4 and 5 were red-shifted by 12 nm and 23 nm,respectively,and the blue fluorescence was observed due to the metal ion perturbation of the ligand luminescence,and the complex quenching of the complex 6.4.The five silver complexes were synthesized by using triphenylphosphine?PPh₃?,2,6-bis?N-methylbenzimidazol-2-yl?-pyridine?mbbp?and2,6-bis?N-allylbenzimidazol-2-yl?-pyridine?abbp?as ligand.They are[Ag₄X₄?PPh₃?₄][X=Cl,?7?;X=Br,?8?;X=I,?9?][Ag₂?mbbp?₂]?pic?₂×DMF×CH₃OH?10?and[Ag₂?abbp?₂Cl₂]_n2n?pic?×CH₃CH₂OH?11?respectively.The ligands and complexes were characterized by IR,¹H NMR and X-ray diffraction.The solid-state fluorescence properties were studied.Finally,the Ag-Ag interaction in the molecule was discussed.The results of the fluorescence experiments show that the silver cluster complexes 7-9 emit fluorescence similar to the ligand PPh₃ under the UV lamp,and the complexes 10 and 11 undergo fluorescence quenching.