Synthesis And Properties Of Thiol-modified Rigid-type Salen Rare Earth Complexes

Lanthanide rare earth ions itself has a unique electronic layer structure,and then with the appropriate organic ligands to form complexes,there are the the following characteristics in optical aspects:stronger emission in the visible region,emission from visible to near-infrared spectrum,stronger ability to absorb energy and higher efficiency of conversion,as a result there are several potential applications for the lanthanum rare earth complexes in optic fiber communications,laser emission and biological imaging and other fields,and gradually it becomes the focus of research.In this paper,Zn-4f and 4f rare earth complexes were synthesized by the reaction between two kinds of rigid Salen ligands decorated by fluorenyl groups(H2L1 and H2L2)and different rare earth salts.And the structure and luminescent properties have been tested and analyzed.The results were as follows:1.A series of homogeneous Zn-4f heteronuclear rare earth complexes LnZnL2Cl(MeOH)[Ln=Nd(1),Gd(2),Er(3),Yb(4)were obtained by the reaction of H2L1,Zn(OAc)2 and rare earth salts.The complexes were tested by IR,UV,MS,thermogravimetric,near infrared luminescence,elemental analysis and single crystal structure.The results indicated that the complexes 1-4 are binuclear sandwich structures,and the complexes 1,3 and 4 showing near-infrared luminescence properties.Then,the ligand H2L1 reacts with rare earth acetate,later a series of binuclear 4f rare earth complexes 5-7[Ln=Nd(5),Er(6),Yb(7)]were obtained.It was found that the complexes 5-7 showing near-infrared luminescence properties.2.A series of homogeneous Zn-4f heteronuclear rare earth complexes 8-11[Ln=Nd(8),Gd(9),Er(10),Yb(11)]were obtained by the reaction of H2L2,Zn(OAc)2 and rare earth salts.The complexes were tested by IR,UV,MS,thermogravimetric,near infrared luminescence,elemental analysis and single crystal structure.The results demonstrated that the complexes 8-10 are binuclear sandwich structures,and the complexes 8,10 and 11 showing near-infrared luminescence properties.Then,the ligand H2L2 reacts with rare earth acetate,later a series of binuclear 4f rare earth complexes 12-14[Ln=Nd(12),Er(13),Yb(14)]were obtained.It was found that the complexes 12-14 showing near-infrared luminescence properties of rare earth ions.And comparing with the reported complexes which has the same coordination environment,we can find that:the lifetimes of Salen-type complexes decorated by fluorenyl groups has increased obviously.