Synthesis,Characterization And Properties Of Cobaltadithiolene Linked Rare Earth Complexes And Terpyridine Derivatives Coordinated Rare Earth Complexes

Metal dithiolene compounds and rare earth compounds have important application value in the fields of optical, electrical and magnetic materials. In this paper, with the aim of preparing the cobaltadithiolene linked rare earth bifunctional complexes, we cariied out the work as below.1. The design and synthesis of cobaltadithiolene linked rare earth bifunctional complexes.According to the literature methods, three new compounds, cobaltadithiolene compounds Ⅰ (Cp*CoS2C2HPy), compound Ⅱ (Cp*CoS2C2(Py)2) and 11,12-bis (isopropylt hio)dipyrido [3,2-a:2’,3’-c] phenazine(Ll) are synthesized. Then six new-rare earth complexes L1-Ln (1a-1f) was obtained by reactions of L1 with rare earth nitrate Ln(NO3)3xH2O (Ln=Sm, Eu, Tb, Dy, Nd, Yb), respectively. All of these new complexes were characterized by IR,1HNMR, MS and elemental analysis. The electrochemical properties of compound Ⅰ and Ⅱ were measured and the UV-visible spectum of compound I was analysed by Density Functional Theory (DFT) method. The luminescent properties of L1-Ln(1a-1f) were also investigated by UV-visible and fluorescence spectra. The results show that the compounds Ⅰ and Ⅱ possess reversible oxidation and reduction properties and may be used as potential electrochemical materials. The fluorescence spectra indicate that the ligand L1 can sensitize the luminescence of Ln3+(Ln=Sm, Eu, Tb, Dy, Nd, Yb), which provides the reference for the preparation of the cobaltadithiolene linked rare earth bifunctional complexes.2. The synthesis of terpyridine derivatives coordinated rare earth complexes.According to the literature methods, one known compound,4’-(4"-methylphen yl)-2,2’:6’,2"-terpyridine (L2) and two new compounds,4’-(N-methyl-4-pyridin-naphthyl)-2,2’:6’,2"-terpyridine (L3),4’-((N-phenyl-methylene-2,2’:6’,2" terpyridine)4-pyridinyl)-2,2’:6’,2"-terpyridine (L4) are synthesized. Then eighteen new rare earth complexes L2-Ln(2a-2f)、L3-Ln (3a-3f)、L4-Ln (4a-4f) are obtained by reactions of L2, L3, L4 with rare earth nitrate Ln(NO3)3xH2O (Ln=Sm, Eu, Tb, Dy, Nd, Yb), respectively. All of these new complexes were characterized by IR,’HNMR, MS and elemental analysis. The luminescent properties of L1-Ln (1a-1f) were also investigated by UV-visible and fluorescence spectra. The fluorescence spectra indicate that the ligand L2 can sensitize the luminescence of Sm3+, Eu3+, Tb3+, Dy3+, Nd3+, Yb3+. However, L3 only can sensitize the luminescence of Eu3+, Tb3+, Yb3+ and L4 only can sensitize the luminescence of Eu3+, Tb3+. It may be caused by the mismatch between the energy level of Sm3+, Dy3+ and L1’s and ligand fluorescence emission masking effect.