Construction Of Novel Complexes With Dipyridinyl Ketone Derivative Ligands Generated In Situ

The construction of coordination complexes with potential application and revealing the relationship between synthetic structure and properties take important roles in coordination chemistry research.The in-situ reactions which can bring especially complexes with unique structure and characteristics attract much attention.In this paper,we selected dipyridyl ketone(L⁰=Dipyridyl ketone)as the main research object to assemble complexes with different metal ions under solvothermal condition.11complexes with different compositions and structures were obtained through the regulation of synthesis conditions,metal ions.According to their composition and structure characteristics,the corresponding properties of some complex were studied.The specific work is as follows:1.The structure and properties of the complexes constructed by dipyridyl ketone derivative were studied.This chapter is divided into three subsections according to the different ligands after in-situ reaction.In the first section,the dipyridyl ketone is reacted in situ to generate the amino derivative ligand HL¹(HL¹=bis(di(pyridin-2-yl)methyl)amine)and two complexes[Cu₂(HL¹)Cl₃]_n(1)and[Cu₂(L¹)Cl₃]·CH₃CN(2).Among them,the meta ions in 1 and 2 are with different in valence state for the the difference in deprotonating of the ligands.1 is a mixed valence with chain structure,while 2 is a dinuclear divalent copper complex.In the second section,ligand H₂L²(H₂L²=di(pyridin-2-yl)methanediol)was obtained by nucleophilic addition one water on the carbonyl group of dipyridyl ketone.The ligands HL² coordinate to metals ions in forming[Cu(H₂L²)₂]Cl₂·2H₂O(3)and[Fe₆(L²)₃(OH)₄Cl₈](6).3 is a purple mononuclear copper complex,in which the copper ion locates in the twisted elongated octahedral coordination geometry.Interestingly,under single crystal to single crystal conversion 3 can transform to a green mononuclear complex[Cu(L⁰)₂Cl₂](4)accompanying with removing 4 water molecules.In 4 the Cl^-ions take the axial position of coordination octahedron replaced that of hydroxyl groups in 3.Further,4 can transform to mononuclear[Cu(H₂L²)₂]Cl₂·4H₂O(5)when placed in a humid environment.5 have similar coordinated environment with 3 but different the H-bonds net.The UV and EPR results also confirmed the different coordination environments of copper ions in 3,4,and 5.In the third subsection,complex[Cd₄(L³)₄Cl₄]·2(H₂O(7),as well,[Ni₅(L⁰)₄Cl₁₀(H₂O)₂]·H₂O(8)was obtained.7 exhibits strong fluorescence emission at 535 nm under the excitation of 320 nm.Magnetic studies show that antiferromagnetic interactions between the Ni^II ions in 8.2.The structure and properties of the complexes constructed based ligand HL⁵(HL⁵=(5-(8-hydroxyquinolin-6-yl)pyridin-2-yl)(pyridin-2-yl)methanone)generated by in-situ coupling of dipyridyl ketone(L⁰)and 8-hydroxyquinoline(HL⁴).Three unique complexes[Ni₈(L⁴)₃(L⁵)₃(SO₄)₃Cl₃]₂·Ni Cl₄(9),[Fe₄(L⁵)₂Cl₆](10)and[Cd₂(L⁵)Cl₃]_n(11)were obtained.9 have an 8-nuclear cation cluster constructed by Ni^II,L⁴,L⁵,sulfate and monodentate Cl^-,and the disordered nickel chloride plays a role in balancing the charge.Further strong antiferromagnetic coupling is found in tetranuclear 10.11 has a chain structure with strong fluorescence emission at 525 nm under the excitation of 345nm.