Construction, Characterization And Properties Of New Aromatic Hydrazone Compounds And Transition Metal Complexes

Aromatic hydrazone compounds is a class of Schiff base compounds, they are prepared by means of condensation from aldehyde or ketone and hydrazide. It has stronger coordination ability and versatile complex style. They have been used to coordinate transition metal to form novel of complexes. And the other is that they have potentially application prospects in fluorescent materials, magnetic materials, analytical reagents, medicine and pesticide and many other areas. It has become a hot research topic.In this paper, There are two new kinds of arylhydrazone ligands:benzylidene acetophenone benzoyl hydrazone (Hbabh) and benzylidene acetophenone-4-chlorobenzoyl hydrazone (Hbacbh). They were synthesized through the condensation of benzylidene acetophenone with hydrazine. Hydrothermal synthesised of eight kinds of aromatic hydrazone transition metal complexes with transition metal (Ni, Cu, Co, Zn), the second pyridine ligand and the ligands which we have been synthesized, and were subsequently developed into single crystal. The compounds were characterized by means of elemental analysis, IR, TGA and the crystal structure was determined by X-ray single crystal diffraction. The compounds which have not been reported are [Ni(babh)2-(py)2],[Cu(babh)2-(py)],[Co(babh)2-(py)2],[Zn(babh)2-(py)2],[Cu(babh)]2,[Ni(bacbh)2-(py)2],[Co(bacbh)2-(py)2],[Cu(bacbh)2-(py)] and five-membered cyclic compound (3,5-diphenyl-4,5-dihydropyrazol-1-yl)-phenyl-methanone. The tests for crystal structure shown that:Hbacbh belongs to the monoclinic system with space group P2(1)/n; five-membered cyclic compound belongs to the orthorhombic system with space group Pca2(1);[Cu(babh)2-(py)] belongs to the monoclinic system with space group P2(1)/c. It shows a pyramid configuration;[Cu(babh)]2belongs to the triclinic system with space group P-1. It shows a double-pyramid configuration;[Cu(bacbh)2-(py)] belongs to the monoclinic system with space group P2(1). It shows a pyramid configuration;[Ni(babh)2-(py)2],[Co(babh)2-(py)2],[Zn(babh)2-(py)2],[Ni(bacbh)2-(py)2] and [Co(bacbh)2-(py)2] all belongs to the monoclinic system with space group P2(1)/n. They show a distorted octahedron configuration. The complex crystal to maintain a certain stability by one-dimensional chain of the compound formed through weak interactions and hydrogen bonds.This paper discussed the two series of aromatic hydrazone complexes hydrothermal synthesis technological conditions. The results shown that:the technological conditions of hydrothermal synthesis of benzylidene acetophenone benzoyl hydrazone transition metal complexes as below, the reaction temperature was140℃, pH=7-8, The suitable solvents of [Ni(babh)2-(py)2] and [Cu(babh)2-(py)] were DMF and acetone, respectively. The suitable solvents of [Co(babh)2-(py)2],[Zn(babh)2-(py)2] and [Cu(babh)]2were methanol. The technological conditions of benzylidene acetophenone-4-chlorobenzoyl hydrazone transition metal complexes as below, the reaction temperature was120℃, pH=7～8, The suitable solvents of [Ni(bacbh)2-(py)2] and [Cu(bacbh)2-(py)] were methanol. The suitable solvents of [Co(bacbh)2-(py)2] was DMF.Fluorescence spectra shown that [Zn(babh)2-(py)2] and the ligand have a certain fluorescence. The ligand exhibits a broad fluorescent emission centered at409nm and436nm. The complex shown more intense photoluminescence with the main emission at463nm. The complex in425nm-475nm fluorescence intensity had been enhanced significantly. So the complex can be used as a potential fluorescent materials.The compound [Cu(babh)]2made Variable-temperature (300-1.8K) magnetic test with a superconducting quantum interference device. It shown that there was ferromagnetic intramolecular interaction and weak antiferromagnetic intermolecular interaction between the dinuclear copper complex CulA…Cul.