多核配合物的合成及结构表征
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摘要
近年来，人们发现多核配合物在生物体内具有独特的生物活性和催化作用。另外，该类配合物在功能材料领域也具有重要的科学意义。因此，多核配合物的合成和结构表征引起了人们的广泛关注。
本硕士学位论文共合成六种多核配合物，并对其结构进行表征。本论文主要由以下五个部分组成：
1．综述了目前多核配合物的发展状况，配合物之间的超分子相互作用，影响配合物自组装的主要因素，以及多核配合物的发展前景。并提出了本论文的研究设想和选题意义。
2．以过渡金属为自旋体，以α，β—不饱和丙烯酸根桥联金属配合物，合成以α-甲基丙烯酸根桥联双核铬配合物，分子间通过氢键堆积成超分子，此配合物是单斜晶系，属P2_1／c空间群，该配合物的晶体结构参数为：a=1.5327(7)nm，b=0.9989(5)nm，c=1.6130(3)nm，β=114.98°。
3．合成了以丙烯酸根桥联双核铜配合物再与乙酰苯胺形成三元配合物。通过红外光谱、紫外光谱、元素分析和x-衍射对单晶进行结构表征。
4．研究并合成氰根桥联双金属配位聚合物K_2[Ni(en)_2][Fe(CN)_6]并对其结构进行表征。研究结果表明该配合物是一维链状超分子化合物，单斜晶系，属C2／c空间群，该配合物的晶体结构参数为：a=1.7010(7)nm，b=0.8061(4)nm，c=1.4430(5)nm，β=109°。
5．研究并合成有机金属配合物与K_3[Cr(CN)_6]自组装成超分子配合物的情况，它们都是以氰根桥联而成的多核配位聚合物。本文合成了两种不同的有机大环配体，它们分别是L_1和L_2，它们的具体结构详见论文相关内容。多核配位聚合物K[Cu(en)_2][Cr(CN)_6]是一维链状超分子化合物，大环铜配合物与[Cr(CN)_6]~(3-)组装成两种新型配合物，它们都是二维网状结构，通过红外光谱、元素分析和x-衍射对单晶结构进行表征。配合物[Cu(L_1)]_2[Cr(CN)_6]_2是三方晶系，属P3空间群，该配合物的晶体结构参数为：a=1.4895(2)nm，b=1.4895(2)nm，c=0.9774(5)nm。配合物[Cu(L_2)]_3[Cr(CN)_6]_2是三斜晶系，属P_1空间群，该配合物的晶体结构参数为：a=0.9251(6)nm，b=1.6405(3)nm，c=1.7801(4)nm，α=113°，β=94°，γ=102°，Z=2。
Recently, it has been found that the multinucleate complexes play an important role in organism due to their unique catalysis and biological activity. In addition, the function material significance of the multinucleate complexes is being discovered. Therefore, the synthesis and structure characterization about these complexes have attracted much attention in science field.
In this dissertation, six novel multinucleate complexes were synthesized by using transition metal ions as spin carries,α,β- unsaturated Carboxylate and cyanide as bridging ligands. The products as-synthesized were characterized by element analyses, IR, UV. With X-ray crystallographic methods, the characterization results of products show that two complexes Cu_2[CH_2=CHCOO]_4(C_8H_9NO)_2 and Cr_2(H_2O)_8(CH_2=C(CH_3)COO)_2Cl_4 are 1D chains by hydrogen bonds, two complexes K[Cu(en)_2][Cr(CN)_6] and K_2[Ni(en)_2][Fe(CN)_6] are one-dimensional chains, and two complexes [Cu(L_1)]_3[Cr(CN)_6]_2 and[Cu(L_2)]_3[Cr(CN)_6]_2 are 2D stair-like layer. The compound of Cr_2(H_2O)_8(CH_2=C(CH_3)COO)_2Cl_4 is Monoclinic Crystal system and P2_1/c space group with a=1.5327(7)nm, b=0.9989(5)nm, c=1.6130(3)nm,β=114.98°, the compound of K_2[Ni(en)_2][Fe(CN)_6] is Monoclinic Crystal system and C2/c space group with a=1.7010(7)nm, b=0.8061(4)nm, c=1.4430(5)nm,β=109°, the compound of [Cu(L_1)]_3[Cr(CN)_6]_2 is Trigonal Crystal system and P3 space group with a=1.4895(2)nm, b=1.4895(2)nm, c=0.9774 (5)nm, and the compound of [Cu(L_2)]_3[Cr(CN)_6]_2 is Triclinic Crystal system and P1 space group with a=0..9251(6)nm, b=1.6405(3)nm, c=1.7801(4)nm,α=113°,β=94°,γ=102°, Z=2.
本硕士学位论文共合成六种多核配合物，并对其结构进行表征。本论文主要由以下五个部分组成：
1．综述了目前多核配合物的发展状况，配合物之间的超分子相互作用，影响配合物自组装的主要因素，以及多核配合物的发展前景。并提出了本论文的研究设想和选题意义。
2．以过渡金属为自旋体，以α，β—不饱和丙烯酸根桥联金属配合物，合成以α-甲基丙烯酸根桥联双核铬配合物，分子间通过氢键堆积成超分子，此配合物是单斜晶系，属P2_1／c空间群，该配合物的晶体结构参数为：a=1.5327(7)nm，b=0.9989(5)nm，c=1.6130(3)nm，β=114.98°。
3．合成了以丙烯酸根桥联双核铜配合物再与乙酰苯胺形成三元配合物。通过红外光谱、紫外光谱、元素分析和x-衍射对单晶进行结构表征。
4．研究并合成氰根桥联双金属配位聚合物K_2[Ni(en)_2][Fe(CN)_6]并对其结构进行表征。研究结果表明该配合物是一维链状超分子化合物，单斜晶系，属C2／c空间群，该配合物的晶体结构参数为：a=1.7010(7)nm，b=0.8061(4)nm，c=1.4430(5)nm，β=109°。
5．研究并合成有机金属配合物与K_3[Cr(CN)_6]自组装成超分子配合物的情况，它们都是以氰根桥联而成的多核配位聚合物。本文合成了两种不同的有机大环配体，它们分别是L_1和L_2，它们的具体结构详见论文相关内容。多核配位聚合物K[Cu(en)_2][Cr(CN)_6]是一维链状超分子化合物，大环铜配合物与[Cr(CN)_6]~(3-)组装成两种新型配合物，它们都是二维网状结构，通过红外光谱、元素分析和x-衍射对单晶结构进行表征。配合物[Cu(L_1)]_2[Cr(CN)_6]_2是三方晶系，属P3空间群，该配合物的晶体结构参数为：a=1.4895(2)nm，b=1.4895(2)nm，c=0.9774(5)nm。配合物[Cu(L_2)]_3[Cr(CN)_6]_2是三斜晶系，属P_1空间群，该配合物的晶体结构参数为：a=0.9251(6)nm，b=1.6405(3)nm，c=1.7801(4)nm，α=113°，β=94°，γ=102°，Z=2。
Recently, it has been found that the multinucleate complexes play an important role in organism due to their unique catalysis and biological activity. In addition, the function material significance of the multinucleate complexes is being discovered. Therefore, the synthesis and structure characterization about these complexes have attracted much attention in science field.
In this dissertation, six novel multinucleate complexes were synthesized by using transition metal ions as spin carries,α,β- unsaturated Carboxylate and cyanide as bridging ligands. The products as-synthesized were characterized by element analyses, IR, UV. With X-ray crystallographic methods, the characterization results of products show that two complexes Cu_2[CH_2=CHCOO]_4(C_8H_9NO)_2 and Cr_2(H_2O)_8(CH_2=C(CH_3)COO)_2Cl_4 are 1D chains by hydrogen bonds, two complexes K[Cu(en)_2][Cr(CN)_6] and K_2[Ni(en)_2][Fe(CN)_6] are one-dimensional chains, and two complexes [Cu(L_1)]_3[Cr(CN)_6]_2 and[Cu(L_2)]_3[Cr(CN)_6]_2 are 2D stair-like layer. The compound of Cr_2(H_2O)_8(CH_2=C(CH_3)COO)_2Cl_4 is Monoclinic Crystal system and P2_1/c space group with a=1.5327(7)nm, b=0.9989(5)nm, c=1.6130(3)nm,β=114.98°, the compound of K_2[Ni(en)_2][Fe(CN)_6] is Monoclinic Crystal system and C2/c space group with a=1.7010(7)nm, b=0.8061(4)nm, c=1.4430(5)nm,β=109°, the compound of [Cu(L_1)]_3[Cr(CN)_6]_2 is Trigonal Crystal system and P3 space group with a=1.4895(2)nm, b=1.4895(2)nm, c=0.9774 (5)nm, and the compound of [Cu(L_2)]_3[Cr(CN)_6]_2 is Triclinic Crystal system and P1 space group with a=0..9251(6)nm, b=1.6405(3)nm, c=1.7801(4)nm,α=113°,β=94°,γ=102°, Z=2.
引文
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[1]王寿武，李宝龙，朱霞，等．氰根桥联超分子配位化学研究进展[J]．化学世界，2004，3(1)：154
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[1]王寿武，李宝龙，朱霞，等．氰根桥联超分子配位化学研究进展[J]．化学世界，2004，3(1)：154
[2]于红梅，戴卫东，王寿武．杂多核氰根桥联配合物的研究进展[J]．河北理工学院学报[J]，2004，26(1)：113
[3]Miyasaka H, Leda H, Matsumoto N, etal. Structure and magnetic properties of the two-dimensional ferromagnetic (Net_4)[{Mn(salen)}_2Fe(CN)_6]: investigation of magnetic anisotropy on a single crystal [J]. Inorg Chem,2003,42:3509
[4]袁爱华，沈小平，郁开北，陆路德，等．新型氰基桥联二维配位聚合物{[Fe(salen)]_2[Ni(CN)_4]}_n的合成、晶体结构和磁性质[J]．化学学报，2003，61(10)：1603
[5]日本化学会．无机化学合成手册[M]．北京：化学工业出版社，1998：308
[6]金斗满，朱文祥．配位化学研究方法[M]．北京：科学出版社，1996：29
[7]陈彦国，廖展如．单核镍配合物的合成、表征和性质[J]．应用化工，2000，29(4)：19
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[9]Shriver D F, Shriver S A, Anderson S E. E.Ligand field strength of the nitroscogen end of cyanide and structures of cubic cyanide polymers [J]. Inorg Chem,1965,25(4):725
[1]高恩庆，唐金魁，冷雪冰，等．三维氢键超分子化合物[H_3cth][Fe(CN)_6].3H_2O的合成与结构[J]．高等学校化学学报，2000，21(5)：663
[2]寇会忠，周北川．氰根桥连配合物的结构与研究[J]．无机化学学报，2004，20(5)：497
[3]Bodie E．Douglas．无机合成[M](第十八卷)．488
[4]曹惠民译．无机化学合成手册[M]．北京：化学工业出版社，1998：310