香豆素Schiff碱配合物的合成、晶体结构及性质研究
发布时间：2018-11-12 09:48
【摘要】：香豆素Schiff碱是一类由含有氨基的香豆素衍生物与活泼羰基的醛、酮脱水缩合而成,最终含有-C=N-双键官能团的化合物。香豆素Schiff碱化合物上的-C=N-双键上的N原子能够提供孤对电子,可以与过渡金属或稀土金属配位,而且形成的配合物结构稳定,性质良好,在催化活性、生物活性、分析化学等诸多领域都有很好的应用前景,因此现在成为配位化学的研究热点之一。本论文先通过在4-羟基香豆素环上硝化得到含-NO2的香豆素,再将-NO2还原生成-NH2,然后再与邻羟基苯甲醛类衍生物反应,得到四个香豆素类Schiff碱配体H2L~1、H2L~2、H2L~3和H2L~4 (H2L~1= 3-[ (5-氯-2-羟基-亚苄基)-氨基]-4-羟基-苯并吡喃-2-酮,H2L~2=3- [ (5-溴-2-羟基-亚苄基)-氨基]-4-羟基-苯并吡喃-2-酮,H2L~3=4-羟基-3-[ (2-羟基-3-甲氧基-亚辛基)-氨基]-苯并吡喃-2-酮,H2L~4=4-羟基-3-[(2-羟基-4-甲氧基-亚辛基)-氨基]-苯并吡喃-2-酮。然后利用配体与过渡金属离子作用,通过自然挥发法,得到6个配合物,分别为[Ni_2(L~1)_2](1)、[Zn_2(L~1)_2].2DMF(2)、[Zn(L~1) 4,4'-Bpy]n(3)、[Ni_2(L~2)_2](4)、[Cu4(L~3)_4](5)、[Mn2(L~4)_2](6)。对它们用元素分析、红外、紫外、荧光进行表征。它们的晶体数据如下:配合物 1:化学组成为 C_(38)H_(34)Cl_2N_4Ni_2O_(12),Mr = 926.67,Monoclinic 晶系,C2/c 空间群,晶胞参数:a= 17.867(5) A,b=9.170(5) (?),c = 24.651(5) (?),α = 90.0°。,β=110.837(5)°, γ=90.00°, Z = 4, V=3775(2)(?)~3, R_1 = 0.0317, = wR_2=0.0761;配合物 2:化学组成为 C_(36)H_(22)Cl_2Zn_2N_4O_(12), Mr =936.34, Monoclinic 晶系,P21/c 空间群,晶胞参数:a = 11.768(3)A,b = 11.011(3) (?),c =15.117(5) (?),α = 90.00°,β=100.769(9)°, γ=90.00°, Z = 2, V= 1924.3(10)(?)~3, R_1 = 0.0728, wR_2 = 0.1970;配合物 3:化学组成为 C_(26)H_(16)CIN_3O_4Zn,Mr = 535.26,Triclinic 晶系,P-1 空间群,晶胞参数:a = 9.791(4) A,b = 11.538(4)(?),c = 14.037(5)(?),α = 78.898(8)°,β= 75.702(9)°,γ = 70.505(9)°,Z = 2,V=1438.0(9)(?)~3,R_1=0.0458,wR_2= 0.1204;配合物 4:化学组成为 C_(38)H_(34)Br_2N_3Ni_2O_(12),Mr = 1015.87,Monoclinic 晶系,C2/c空间群,晶胞参数:a = 17.993(4)A,b = 9.2095(18)A， c=24.969(6)A，，α = 90.000=110.249(2)°, γ = 90.00 °, Z = 4, V= 3881.8(15) (?)~3, Ri = 0.0444, wR_2 = 0.1083;配合物 5:化学组成为 C_(68)H_(44)Cu_4N_4O_2O, Mr =1491.27, Tetragonal 晶系,I41/a 空间群,晶胞参数:α =16.633(4)A,b=16.633(4) (?),c = 23.429(4α=β=γ = 90.00°,Z=4, V= 6482(3)(?)~3, Ri = 0.0396, wR_2 = 0.1002;配合物 6:化学组成为 C_(38)H_(38)N_2Mn_2O_(14),Mr = 856.58,Triclinic 晶系,P-1 空间群,晶胞参数:a = 8.2828(12)A,b= 10.428(2)(?),c = 12.152(3)A, α = 113.44(2)°,β=93.369(16)°, γ = 107.890(16) °, Z=1, V= 896.5(4)(?)~3, R_1 = 0.0581, wR_2 = 0.1002;
[Abstract]:Coumarin Schiff base is a kind of compound which consists of coumarin derivatives containing amino group and active carbonyl aldehyde and ketone. In coumarin Schiff base compounds, the N atoms on the -C ~ (2 +) N ~ (-) -double bond can provide lone pair electrons and can coordinate with transition metal or rare earth metal, and the complexes formed are stable in structure, good in properties, and in catalytic activity and biological activity. Analytical chemistry and many other fields have good application prospects, so it has become one of the research hotspots in coordination chemistry. In this paper, the coumarin containing-NO2 was obtained by nitration on the 4-hydroxycoumarin ring, then-NH2, was reduced to-NH2, and then reacted with o-hydroxybenzaldehyde derivatives. Four coumarin Schiff ligands H _ 2L ~ (1) and H _ (2) L ~ (2) were obtained. H2L~3 and H2L~4 (H2L1 = 3- [(5-chloro-2-hydroxy-benzylidene) -amino] -4-hydroxy-benzopyran-2-one, H _ 2L _ 2N _ 3- [(5-bromo-2-hydroxy-benzylidene) -amino] -4-hydroxy-benzopyran-2-one, H _ 2LU _ 3N _ 4H-3- [(2-hydroxy-3-methoxy-n-octyl) -amino] -benzopyran-2-one, H _ 2L _ 2O _ 4-hydroxy-3- [(2-hydroxy-4-methoxy-octyl) -amino] -benzopyran -2-one. Then, six complexes, [Ni_2 (L1) 2] (1), [Zn_2 (L1) 2]. 2DMF (2), were obtained by the natural volatilization method by using ligands and transition metal ions. N (3), [Ni_2 (Ln2) 2] (4), [Cu4 (LK3) 4] (5), [Mn2 (LK4) 2] (6). They were characterized by elemental analysis, IR, UV and fluorescence. Their crystal data are as follows: complex 1: chemical composition C _ (38) H _ (34) Cl_2N_4Ni_2O_ (12), Mr = 926.67) Monoclinic crystal system, C _ 2 / c space group, unit cell parameter: a = 17.867 (5) A. Bang 9.170 (5) (?), c = 24.651 (5) (?), 伪 = 90.0 掳., 尾 = 110.837 (5) 掳, 纬 = 90.00 掳, Z = 4, VN 3775 (2) (?) ~ 3, Raven1 = 0.0317, = wR_2=0.0761; Complex 2: C _ (36) H _ (22) Cl_2Zn_2N_4O_ (12), Mr = 936.34, Monoclinic crystal system, P21 / c space group, unit cell parameter: a = 11.768 (3) Agnb = 11.011 (3) (?), C = 15.117 (5) (?), 伪 = 90.00 掳, 尾 = 100.769 (9) 掳, 纬 = 90.00 掳, Z = 2, V = 1924.3 (10) (?) ~ 3, wR_2 1 = 0.0728, wR_2 = 0.197; The chemical composition of complex 3 is C _ (26) H _ (16) CIN_3O_4Zn,Mr = 535.26 Triclinic crystal system, P-1 space group, unit cell parameter: a = 9.791 (4) Agnb = 11.538 (4) (?), C = 14.037 (5) (?), 伪 = 78.898 (8) 掳, 尾 = 75.702 (9) 掳, 纬 = 70.505 (9) 掳, Z = 2VX 1438.0 (? The chemical composition of complex 4 is C _ (38) H _ (34) Br_2N_3Ni_2O_ (12), Mr = 1015.87) Monoclinic crystal system, C _ 2 / c space group, unit cell parameter: a = 17.993 (4) Anb = 9.2095 (18) A. C = 24.969 (6) A, 伪 = 90.000,110.249 (2) 掳, 纬 = 90.00 掳, Z = 4, V = 3881.8 (15) (?) ~ 3, Ri = 0.0444, wR_2 = 0.1083; The chemical composition of complex 5 is C _ (68) H _ (44) Cu_4N_4O_2O, Mr = 1491.27, Tetragonal crystal system, I _ 41 / a space group, unit cell parameter 伪 = 16.633 (4) Agna 16.633 (4) (?), C = 23.429 (4 伪 = 尾 = 纬 = 90.00 掳, Z 4, V = 6482 (3) (?) ~ 3, Ri = 0.0396, wR_2 = 0.1002; Complex 6: chemical composition of C38 H38 N2Mn2O14), Mr = 856.58 Triclinic crystal system, P-1 space group, unit cell parameter: a = 8.2828 (12) Agnb = 10.428 (2) (?), C = 12.152 (3) A, 伪 = 113.44 (2) 掳, 尾 = 93.369 (16) 掳, 纬 = 107.890 (16) 掳, Z 1, V = 896.5 (4) (?) ~ 3, wR_2 1 = 0.0581, wR_2 = 0.1002;
【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：2326759
[Abstract]:Coumarin Schiff base is a kind of compound which consists of coumarin derivatives containing amino group and active carbonyl aldehyde and ketone. In coumarin Schiff base compounds, the N atoms on the -C ~ (2 +) N ~ (-) -double bond can provide lone pair electrons and can coordinate with transition metal or rare earth metal, and the complexes formed are stable in structure, good in properties, and in catalytic activity and biological activity. Analytical chemistry and many other fields have good application prospects, so it has become one of the research hotspots in coordination chemistry. In this paper, the coumarin containing-NO2 was obtained by nitration on the 4-hydroxycoumarin ring, then-NH2, was reduced to-NH2, and then reacted with o-hydroxybenzaldehyde derivatives. Four coumarin Schiff ligands H _ 2L ~ (1) and H _ (2) L ~ (2) were obtained. H2L~3 and H2L~4 (H2L1 = 3- [(5-chloro-2-hydroxy-benzylidene) -amino] -4-hydroxy-benzopyran-2-one, H _ 2L _ 2N _ 3- [(5-bromo-2-hydroxy-benzylidene) -amino] -4-hydroxy-benzopyran-2-one, H _ 2LU _ 3N _ 4H-3- [(2-hydroxy-3-methoxy-n-octyl) -amino] -benzopyran-2-one, H _ 2L _ 2O _ 4-hydroxy-3- [(2-hydroxy-4-methoxy-octyl) -amino] -benzopyran -2-one. Then, six complexes, [Ni_2 (L1) 2] (1), [Zn_2 (L1) 2]. 2DMF (2), were obtained by the natural volatilization method by using ligands and transition metal ions. N (3), [Ni_2 (Ln2) 2] (4), [Cu4 (LK3) 4] (5), [Mn2 (LK4) 2] (6). They were characterized by elemental analysis, IR, UV and fluorescence. Their crystal data are as follows: complex 1: chemical composition C _ (38) H _ (34) Cl_2N_4Ni_2O_ (12), Mr = 926.67) Monoclinic crystal system, C _ 2 / c space group, unit cell parameter: a = 17.867 (5) A. Bang 9.170 (5) (?), c = 24.651 (5) (?), 伪 = 90.0 掳., 尾 = 110.837 (5) 掳, 纬 = 90.00 掳, Z = 4, VN 3775 (2) (?) ~ 3, Raven1 = 0.0317, = wR_2=0.0761; Complex 2: C _ (36) H _ (22) Cl_2Zn_2N_4O_ (12), Mr = 936.34, Monoclinic crystal system, P21 / c space group, unit cell parameter: a = 11.768 (3) Agnb = 11.011 (3) (?), C = 15.117 (5) (?), 伪 = 90.00 掳, 尾 = 100.769 (9) 掳, 纬 = 90.00 掳, Z = 2, V = 1924.3 (10) (?) ~ 3, wR_2 1 = 0.0728, wR_2 = 0.197; The chemical composition of complex 3 is C _ (26) H _ (16) CIN_3O_4Zn,Mr = 535.26 Triclinic crystal system, P-1 space group, unit cell parameter: a = 9.791 (4) Agnb = 11.538 (4) (?), C = 14.037 (5) (?), 伪 = 78.898 (8) 掳, 尾 = 75.702 (9) 掳, 纬 = 70.505 (9) 掳, Z = 2VX 1438.0 (? The chemical composition of complex 4 is C _ (38) H _ (34) Br_2N_3Ni_2O_ (12), Mr = 1015.87) Monoclinic crystal system, C _ 2 / c space group, unit cell parameter: a = 17.993 (4) Anb = 9.2095 (18) A. C = 24.969 (6) A, 伪 = 90.000,110.249 (2) 掳, 纬 = 90.00 掳, Z = 4, V = 3881.8 (15) (?) ~ 3, Ri = 0.0444, wR_2 = 0.1083; The chemical composition of complex 5 is C _ (68) H _ (44) Cu_4N_4O_2O, Mr = 1491.27, Tetragonal crystal system, I _ 41 / a space group, unit cell parameter 伪 = 16.633 (4) Agna 16.633 (4) (?), C = 23.429 (4 伪 = 尾 = 纬 = 90.00 掳, Z 4, V = 6482 (3) (?) ~ 3, Ri = 0.0396, wR_2 = 0.1002; Complex 6: chemical composition of C38 H38 N2Mn2O14), Mr = 856.58 Triclinic crystal system, P-1 space group, unit cell parameter: a = 8.2828 (12) Agnb = 10.428 (2) (?), C = 12.152 (3) A, 伪 = 113.44 (2) 掳, 尾 = 93.369 (16) 掳, 纬 = 107.890 (16) 掳, Z 1, V = 896.5 (4) (?) ~ 3, wR_2 1 = 0.0581, wR_2 = 0.1002;
【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
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