Salamo型3d-4f金属配合物的合成、晶体结构及荧光性质研究
发布时间：2019-03-18 17:41
【摘要】：Salen型金属配合物在生物、催化、磁性材料等领域均有广泛的应用研究,特别是Salen型3d-4f配合物近年来成为配位化学的热点,是材料领域的研究重点之一。通过Salen型配体衍生出的Salamo型配体,因其更稳定的螯合功能可形成结构更多样更复杂的金属配合物。为了进一步研究Salamo型3d-4f异金属配合物的合成、晶体结构及光物理性能,本文设计并成功合成了Salamo型双肟配体H2L以及六种3d-4f异核双金属配合物[Zn(L)(OAc)Sm(NO3)2](1),[Zn(L)(OAc)Eu(NO3)2](2),[Zn(L)(OAc)Tb(NO3)2](3),[Zn(L)(OAc)Dy(NO3)2](4),[Cu(L)Nd(NO3)2(C2H5OH)](5),[Zn(L)(OAc)Ce(NO3)2(CH3OH)](6)。配合物1:化学组成为C22H25SmN4O14Zn,Mr=785.18,属于单斜晶系,空间群P21/n,晶胞参数:a=13.1508(10)?,b=13.2882(9)?,c=16.3883(9)?,β=104.519(7)°,Z=4,V=2772.4(3)?3,R1=0.0724,wR2=0.0931;配合物2:化学组成为C22H25EuN4O14Zn,Mr=786.82,属于单斜晶系,空间群P21/n,晶胞参数:a=13.1508(7)?,b=13.2769(5)?,c=16.3725(9)?,β=104.442(6)°,Z=4,V=2768.3(2)?3,R1=0.0490,wR2=0.0639;配合物3:化学组成为C22H25TbN4O14Zn,Mr=793.75,属于单斜晶系,空间群P21/n,晶胞参数:a=13.1130(6)?,b=13.2655(5)?,c=16.3649(7)?,β=104.340(5)°,Z=4,V=2758.0(2)?3,R1=0.0386,wR2=0.0610;配合物4:化学组成为C22H25DyN4O14Zn,Mr=797.33,属于单斜晶系,空间群P21/n,晶胞参数:a=13.0950(5)?,b=13.2699(4)?,c=16.3621(6)?,β=104.270(4)°,Z=4,V=2755.52(17)?3,R1=0.0337,wR2=0.0563;配合物5:化学组成为C22H28NdN5O16Cu,Mr=826.27,属于单斜晶系,空间群P21/n,晶胞参数:a=9.4291(3)?,b=15.2896(4)?,c=21.3512(4)?,β=92.353(2)°,Z=4,V=3075.55(14)?3,R1=0.0352,wR2=0.0587;配合物6:化学组成为C23H29CeN4O15Zn,Mr=806.99,属于三斜晶系,空间群P1,晶胞参数:a=9.0577(8)?,b=12.0332(13)?,c=15.4757(13)?,α=99.496(8)°,β=102.562(7)°,γ=111.854(9)°,Z=2,V=1470.7(3)?3,R1=0.0345,wR2=0.0649;通过核磁氢谱、元素分析、红外光谱等方法对得到的配体和配合物进行表征,利用X-射线晶体衍射法确定配合物结构,并对ZnIILnIII(Ln=Sm,Eu,Tb,Dy)配合物的荧光性质和磁性进行了初步分析,对其发光机理展开初步探讨。
[Abstract]:Salen-type metal complexes have been widely used in the fields of biology, catalysis, magnetic materials and so on. Especially, Salen-type 3d-4f complexes have become a hot spot in coordination chemistry in recent years and become one of the research focuses in the field of materials. Salamotype ligands derived from Salen ligands can form more diverse and complex metal complexes because of their more stable chelating function. In order to further study the synthesis, crystal structure and photophysical properties of Salamotype 3d-4f heterometallic complexes, Salamotype dioxime ligand H2L and six 3d-4f heteronuclear bimetallic complexes [Zn (L) (OAc) Sm (NO3) 2] (1), [Zn (L) (OAc) Eu (NO3) 2] (2) were designed and synthesized. [Zn (L) (OAc) Tb (NO3) 2] (3), [Zn (L) (OAc) Dy (NO3) 2] (4), [Cu (L) Nd (NO3) 2 (C2H5OH)] (5), [Zn (L) (OAc) Ce (NO3) 2 (CH3OH)] (6). Complex 1: the chemical group is C22H25SmN4O14Zn, Mrx785.18, belongs to monoclinic system, the space group P21um, the unit cell parameters: a, 13. 1508 (10)?, b, 13. 2882 (9)?, c, 16. 3883 (9)?, 尾 = 104.519 (7) 掳, Z, 4, V = 2772.4 (3)? 3, R1 / 0.0724, wR2 / 0.0931; Complex 2: the chemical group is C22H25EUN4O14Zn, Mrx786.82, belongs to monoclinic system, the space group P21um, the unit cell parameters: a, 13.1508 (7)?, b, 13.2769 (5)?, c, 16.3725 (9)?, 尾 = 104.442 (6) 掳, Z, 4, V = 2768.3 (2)? 3, R1 / 0.0490, wR2 / 0.0639; Complex 3: the chemical group is C22H25TbN4O14Zn, Mrx793.75, belongs to monoclinic system, the space group P21um, the cell parameters: a, 13.1130 (6)?, b, 13.2655 (5)?, c, 16.3649 (7)?, 尾 = 104.340 (5) 掳, Z, 4, V = 2758.0 (2)? 3, R1 / 0.0386, wR2 / 0.0610; Complex 4: the chemical group is C22H25DyN4O14Zn, Mrx797.33, belongs to monoclinic system, the space group P21um, the unit cell parameters: a, 13.0950 (5)?, b, 13.2699 (4)?, c = 16.3621 (6)?, 尾 = 104.270 (4) 掳, Z, 4, V = 2755.52 (17)? 3, R1 / 0.0337, wR2 / 0.0563; Complex 5: the chemical composition is C22H28NdN5O16Cu, Mrx826.27, belongs to monoclinic system, the space group P21um, the cell parameters: a, 9. 4291 (3)?, b, 15. 2896 (4)?, c, 21. 3512 (4)?, 尾 = 92.353 (2) 掳, Z, 4, Va 3075.55 (14)? 3, R1 / 0.0352, wR2 / 0.0587; Complex 6: the chemical composition is C23H29CeN4O15Zn, Mrs, 806.99, belongs to the triclinic system, space group P1, the cell parameters: a, 9.0577 (8)?, (b) 12.0332 (13)?, (c) 15.4757 (13)?, 伪 = 99.496 (8) 掳, 尾 = 102.562 (7) 掳, 伪 = 99.496 (8) 掳, 尾 = 102.562 (7) 掳, 伪 = 99.496 (8) 掳, 尾 = 102.562 (7) 掳, 纬 = 111.854 (9) 掳, Z 2, V = 1470.7 (3)? 3, R1 / 0.0345, wR2 / 0.0649; The ligands and complexes were characterized by NMR, elemental analysis and infrared spectroscopy. The structure of the complexes was determined by X-ray crystal diffraction and ZnIILnIII (Ln=Sm,Eu,Tb,). The fluorescence properties and magnetic properties of Dy) complexes were analyzed, and the luminescence mechanism of the complexes was discussed.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
本文编号：2443073
[Abstract]:Salen-type metal complexes have been widely used in the fields of biology, catalysis, magnetic materials and so on. Especially, Salen-type 3d-4f complexes have become a hot spot in coordination chemistry in recent years and become one of the research focuses in the field of materials. Salamotype ligands derived from Salen ligands can form more diverse and complex metal complexes because of their more stable chelating function. In order to further study the synthesis, crystal structure and photophysical properties of Salamotype 3d-4f heterometallic complexes, Salamotype dioxime ligand H2L and six 3d-4f heteronuclear bimetallic complexes [Zn (L) (OAc) Sm (NO3) 2] (1), [Zn (L) (OAc) Eu (NO3) 2] (2) were designed and synthesized. [Zn (L) (OAc) Tb (NO3) 2] (3), [Zn (L) (OAc) Dy (NO3) 2] (4), [Cu (L) Nd (NO3) 2 (C2H5OH)] (5), [Zn (L) (OAc) Ce (NO3) 2 (CH3OH)] (6). Complex 1: the chemical group is C22H25SmN4O14Zn, Mrx785.18, belongs to monoclinic system, the space group P21um, the unit cell parameters: a, 13. 1508 (10)?, b, 13. 2882 (9)?, c, 16. 3883 (9)?, 尾 = 104.519 (7) 掳, Z, 4, V = 2772.4 (3)? 3, R1 / 0.0724, wR2 / 0.0931; Complex 2: the chemical group is C22H25EUN4O14Zn, Mrx786.82, belongs to monoclinic system, the space group P21um, the unit cell parameters: a, 13.1508 (7)?, b, 13.2769 (5)?, c, 16.3725 (9)?, 尾 = 104.442 (6) 掳, Z, 4, V = 2768.3 (2)? 3, R1 / 0.0490, wR2 / 0.0639; Complex 3: the chemical group is C22H25TbN4O14Zn, Mrx793.75, belongs to monoclinic system, the space group P21um, the cell parameters: a, 13.1130 (6)?, b, 13.2655 (5)?, c, 16.3649 (7)?, 尾 = 104.340 (5) 掳, Z, 4, V = 2758.0 (2)? 3, R1 / 0.0386, wR2 / 0.0610; Complex 4: the chemical group is C22H25DyN4O14Zn, Mrx797.33, belongs to monoclinic system, the space group P21um, the unit cell parameters: a, 13.0950 (5)?, b, 13.2699 (4)?, c = 16.3621 (6)?, 尾 = 104.270 (4) 掳, Z, 4, V = 2755.52 (17)? 3, R1 / 0.0337, wR2 / 0.0563; Complex 5: the chemical composition is C22H28NdN5O16Cu, Mrx826.27, belongs to monoclinic system, the space group P21um, the cell parameters: a, 9. 4291 (3)?, b, 15. 2896 (4)?, c, 21. 3512 (4)?, 尾 = 92.353 (2) 掳, Z, 4, Va 3075.55 (14)? 3, R1 / 0.0352, wR2 / 0.0587; Complex 6: the chemical composition is C23H29CeN4O15Zn, Mrs, 806.99, belongs to the triclinic system, space group P1, the cell parameters: a, 9.0577 (8)?, (b) 12.0332 (13)?, (c) 15.4757 (13)?, 伪 = 99.496 (8) 掳, 尾 = 102.562 (7) 掳, 伪 = 99.496 (8) 掳, 尾 = 102.562 (7) 掳, 伪 = 99.496 (8) 掳, 尾 = 102.562 (7) 掳, 纬 = 111.854 (9) 掳, Z 2, V = 1470.7 (3)? 3, R1 / 0.0345, wR2 / 0.0649; The ligands and complexes were characterized by NMR, elemental analysis and infrared spectroscopy. The structure of the complexes was determined by X-ray crystal diffraction and ZnIILnIII (Ln=Sm,Eu,Tb,). The fluorescence properties and magnetic properties of Dy) complexes were analyzed, and the luminescence mechanism of the complexes was discussed.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4
【参考文献】
相关期刊论文 前1条
1 Jean-Claude G. Bünzli;Svetlana V. Eliseeva;;Lanthanide NIR luminescence for telecommunications, bioanalyses and solar energy conversion[J];Journal of Rare Earths;2010年06期
相关博士学位论文 前1条
1 高婷;Salen金属配合物的合成、荧光及分子磁性的研究[D];黑龙江大学;2008年
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