A new binuclear cage-like yttrium(Ⅲ) complex Y2(TMBA)6(phen)2(1) with yttrium nitrate, 2,4,6-trimethylbenzoic acid(TMBA) and 1,10-phenanthroline(phen) was synthesized. It crystallizes in the triclinic space group P1 ...A new binuclear cage-like yttrium(Ⅲ) complex Y2(TMBA)6(phen)2(1) with yttrium nitrate, 2,4,6-trimethylbenzoic acid(TMBA) and 1,10-phenanthroline(phen) was synthesized. It crystallizes in the triclinic space group P1 with a = 11.9086(15), b = 12.4843(17), c = 14.2101(18) ?, α = 104.977(4), β = 111.750(4), γ = 95.874(5)o, V = 1848.8(4) ?3, Dc = 1.363 g/cm3, Z = 1, μ(Mo Ka) = 1.627, F(000) = 788, the final GOOF = 1.039, R = 0.0353 and w R = 0.0826. The whole molecule consists of two yttrium ions bridged by four 2,4,6-trimethylbenzoic acid anions. The Y(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The TG analysis and fluorescent properties of 1 were studied.展开更多
The magnetic coupling interactions of the nitronyl nitroxide radicals bound to diamagnetic(YⅢ) and paramagnetic(GdⅢ) rare earth ions in two model magnetic systems based on novel rare earth organic radical complexes ...The magnetic coupling interactions of the nitronyl nitroxide radicals bound to diamagnetic(YⅢ) and paramagnetic(GdⅢ) rare earth ions in two model magnetic systems based on novel rare earth organic radical complexes Ln(hfac)3(NITPhOCH3)2(Ln=YⅢ 1,GdⅢ 2;hafc = hexafluoroacetylacetonate;NIT-PhOCH3 = 4'-methoxyo-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been investigated by density functional theory(DFT).The magnetic coupling mechanisms were also explored from the viewpoint of molecular orbital and spin density populations.DFT calculations show that the empty 4d-orbitals of YⅢ and 5d-orbitals of GdⅢ play an important role in the antiferromagnetic coupling between the two nitronyl nitroxide radical ligands,and that the ferromagnetic coupling between the GdⅢ ion and the radical magnetic centers can be attributed to the nearly complete localization of the isotropic 4f-shell and singly occupied magnetic orbital(π) of the nitronyl nitroxide.展开更多
基金Supported by Natural Science Foundation of Hunan Province (2019JJ60021)Industry and Research Key Project of Hengyang City (2019jhzx1093,2018kKJ016)。
文摘A new binuclear cage-like yttrium(Ⅲ) complex Y2(TMBA)6(phen)2(1) with yttrium nitrate, 2,4,6-trimethylbenzoic acid(TMBA) and 1,10-phenanthroline(phen) was synthesized. It crystallizes in the triclinic space group P1 with a = 11.9086(15), b = 12.4843(17), c = 14.2101(18) ?, α = 104.977(4), β = 111.750(4), γ = 95.874(5)o, V = 1848.8(4) ?3, Dc = 1.363 g/cm3, Z = 1, μ(Mo Ka) = 1.627, F(000) = 788, the final GOOF = 1.039, R = 0.0353 and w R = 0.0826. The whole molecule consists of two yttrium ions bridged by four 2,4,6-trimethylbenzoic acid anions. The Y(Ⅲ) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The TG analysis and fluorescent properties of 1 were studied.
基金Supported by the 973 Project (Grant No. 2006CB601102)the National Natural Science Foundation of China (Grant No. 20973052)
文摘The magnetic coupling interactions of the nitronyl nitroxide radicals bound to diamagnetic(YⅢ) and paramagnetic(GdⅢ) rare earth ions in two model magnetic systems based on novel rare earth organic radical complexes Ln(hfac)3(NITPhOCH3)2(Ln=YⅢ 1,GdⅢ 2;hafc = hexafluoroacetylacetonate;NIT-PhOCH3 = 4'-methoxyo-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been investigated by density functional theory(DFT).The magnetic coupling mechanisms were also explored from the viewpoint of molecular orbital and spin density populations.DFT calculations show that the empty 4d-orbitals of YⅢ and 5d-orbitals of GdⅢ play an important role in the antiferromagnetic coupling between the two nitronyl nitroxide radical ligands,and that the ferromagnetic coupling between the GdⅢ ion and the radical magnetic centers can be attributed to the nearly complete localization of the isotropic 4f-shell and singly occupied magnetic orbital(π) of the nitronyl nitroxide.
