【摘要】：香豆素Schiff堿是一類(lèi)由含有氨基的香豆素衍生物與活潑羰基的醛、酮脫水縮合而成,最終含有-C=N-雙鍵官能團(tuán)的化合物。香豆素Schiff堿化合物上的-C=N-雙鍵上的N原子能夠提供孤對(duì)電子,可以與過(guò)渡金屬或稀土金屬配位,而且形成的配合物結(jié)構(gòu)穩(wěn)定,性質(zhì)良好,在催化活性、生物活性、分析化學(xué)等諸多領(lǐng)域都有很好的應(yīng)用前景,因此現(xiàn)在成為配位化學(xué)的研究熱點(diǎn)之一。本論文先通過(guò)在4-羥基香豆素環(huán)上硝化得到含-NO2的香豆素,再將-NO2還原生成-NH2,然后再與鄰羥基苯甲醛類(lèi)衍生物反應(yīng),得到四個(gè)香豆素類(lèi)Schiff堿配體H2L~1、H2L~2、H2L~3和H2L~4 (H2L~1= 3-[ (5-氯-2-羥基-亞芐基)-氨基]-4-羥基-苯并吡喃-2-酮,H2L~2=3- [ (5-溴-2-羥基-亞芐基)-氨基]-4-羥基-苯并吡喃-2-酮,H2L~3=4-羥基-3-[ (2-羥基-3-甲氧基-亞辛基)-氨基]-苯并吡喃-2-酮,H2L~4=4-羥基-3-[(2-羥基-4-甲氧基-亞辛基)-氨基]-苯并吡喃-2-酮。然后利用配體與過(guò)渡金屬離子作用,通過(guò)自然揮發(fā)法,得到6個(gè)配合物,分別為[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)。對(duì)它們用元素分析、紅外、紫外、熒光進(jìn)行表征。它們的晶體數(shù)據(jù)如下:配合物 1:化學(xué)組成為 C_(38)H_(34)Cl_2N_4Ni_2O_(12),Mr = 926.67,Monoclinic 晶系,C2/c 空間群,晶胞參數(shù):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:化學(xué)組成為 C_(36)H_(22)Cl_2Zn_2N_4O_(12), Mr =936.34, Monoclinic 晶系,P21/c 空間群,晶胞參數(shù):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:化學(xué)組成為 C_(26)H_(16)CIN_3O_4Zn,Mr = 535.26,Triclinic 晶系,P-1 空間群,晶胞參數(shù):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:化學(xué)組成為 C_(38)H_(34)Br_2N_3Ni_2O_(12),Mr = 1015.87,Monoclinic 晶系,C2/c空間群,晶胞參數(shù):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:化學(xué)組成為 C_(68)H_(44)Cu_4N_4O_2O, Mr =1491.27, Tetragonal 晶系,I41/a 空間群,晶胞參數(shù):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:化學(xué)組成為 C_(38)H_(38)N_2Mn_2O_(14),Mr = 856.58,Triclinic 晶系,P-1 空間群,晶胞參數(shù):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) (?), 偽 = 90.0 擄., 尾 = 110.837 (5) 擄, 緯 = 90.00 擄, 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) (?), 偽 = 90.00 擄, 尾 = 100.769 (9) 擄, 緯 = 90.00 擄, 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) (?), 偽 = 78.898 (8) 擄, 尾 = 75.702 (9) 擄, 緯 = 70.505 (9) 擄, 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, 偽 = 90.000,110.249 (2) 擄, 緯 = 90.00 擄, 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 偽 = 16.633 (4) Agna 16.633 (4) (?), C = 23.429 (4 偽 = 尾 = 緯 = 90.00 擄, 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, 偽 = 113.44 (2) 擄, 尾 = 93.369 (16) 擄, 緯 = 107.890 (16) 擄, Z 1, V = 896.5 (4) (?) ~ 3, wR_2 1 = 0.0581, wR_2 = 0.1002;
【學(xué)位授予單位】：蘭州交通大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.4

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