以氮杂环为配体的配合物的合成、结构及性质研究

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英文题名：Synthesis, Structure and Properties of Coordination Complexes Supported by Nitrogen-containing Heterocyclic Ligands 作者：陈砚美 论文级别：博士 学科专业名称：无机化学 中文关键词：咪唑并[1 ; 5-a]吡啶 ; 吡啶二羧酸 ; 碱土金属 ; 荧光 ; 磁性 英文关键词：imidazo[1 ; 5-a]pyridine ; pyridine dicarboxylic acid ; alkaline earth metal ; fluorescence ; magnetism 学位年度：2014 导师：李亚红 学科代码：070301 学位授予单位：苏州大学 论文提交日期：2014-06-01

摘要

含氮杂环配合物作为杂环配合物的一种，因其多变的结构、良好的生物活性和较强的配位能力，一直受到配位化学家们的青睐。随着配位化学的发展，咪唑、吡啶、吡唑、吡咯等含氮杂环类配体已经被大量应用到配合物中。用这些配体构架出来的配合物具有迷人的结构和在荧光、催化、吸附、磁性材料等方面有广阔的应用。本论文中，我们致力于合成以吡啶衍生物为配体的配合物，并研究它们的化学、物理性质。本论文主要选取3-吡啶基咪唑并[1,5-a]吡啶为配体，使其和不同醛在金属离子的作用下，通过原位金属/配体反应得到了一系列结构新颖的配合物，并提出了该原位反应的机理。另外，以四种吡啶二羧酸为配体合成了一系列碱土-稀土金属杂核的配合物和碱土-过渡金属杂核的配合物，并根据这些配合物的结构特点，分别研究了相应配合物的荧光和磁性质。主要结果简述如下：
     1.我们设计了一系列吡啶甲醛、醋酸铵和过渡金属离子在溶剂热条件下的反应，得到了5个原位反应配体L1, L2, L3, L4, L5和14个结构新颖的配合物。Fe(L1)Cl2(1), Fe2(L2)Cl4(2),Fe2(L3)Cl4·EtOH (3), Fe(L4)Cl2(4), Co(L1)Cl2·0.5EtOH (5), Co2(L2)Cl4(6), Co2(L3)Cl4·EtOH (7),Co(L5)Cl2(8),[CuI2(L2)Cl2]In(9),[CuII(L3)Cl][CuICl2]·2EtOH (10),[CuII4(L3)Cl5][Cu2Cl3·2(CuICl2)](11), Cu(L4)Cl·EtOH (12),[L4CuCl]+·[Cu-2-2Cl3](13),2[HL4CuCl]2+·2(CuCl2)-·[CuCl3]·2H2O (14)。这些配合物的结构可以通过调节起始原料的种类和原料比例来控制。这些合成最显著的特点是实现了将吡啶甲醛的醛基可控地分别转化成了酮、亚甲基、叔碳和季碳中心。
     2.我们研究了CuCl2·2H2O（或CuBr2·2H2O）和HPIP（HPIP=3-吡啶基咪唑并[1,5-a]吡啶）分别与甲醛、甲酸、N,N-二甲基甲酰胺（DMF）和乙二醛，在乙酸存在/不存在时的反应。我们发现在CuII存在下，HPIP和甲醛、甲酸、DMF和乙二醛分别反应可以得到以咪唑并[1,5-a]吡啶衍生物为配体的配合物。得到了六个结构新颖的配合物[L6Cu2Cl2][Cu2Cl4]·2EtOH (15),[L6Cu2Br2][Cu2Br4]·2EtOH (16),[(L7)2Cu3](CuCl2)3·2EtOH (17),2{[(L7)2Cu3](CuBr2)3}·EtOH (18),L8Cu2Cl2(19)和L8Cu2Br2(20)。并在研究其原位反应原理的过程中得到了[L6Co2Cl4]·2EtOH (21),[Co2(HPIP)2Cl4](22),[Cu2(HPIP)2Cu2Cl4](23)和L9ZnCl2(24)四种配合物和新配体L9的晶体。
     3.以2,6-吡啶二甲酸为配体，和稀土离子盐、SrCl2·6H2O或Sr(OH)2·8H2O反应，通过调节体系中咪唑的量，合成了21个配位聚合物：[Sr3(pydc)2(Hpydc)2(H2O)2]n·2nH2O (25),[Dy3Sr3(pydc)7(Hpydc)(H2O)9]·6H2O (26),[Ln2Sr3(pydc)6(H2O)18]·nH2O (Ln=Sm (27), Eu (28), n=11; Gd (29), n=16; Tb (30), Dy (31), n=13),[LnSr(pydc)3(H2O)5]·Him·H2O (Ln=Sm(32), Eu (33),Gd (34), Tb (35), Dy(36)),[Ln2Sr(pydc)6(H2O)5]·4Him·C2H5OH·nH2O (Ln=Sm(37), n=4; Eu (38), n=5; Gd (39), n=4; Dy(40) n=5),[LnSr(pydc)3(H2O)4]·Him·3H2O (Ln=Gd (41), Tb (42) Dy (43)),[GdSr(pydc)3(H2O)5]·Him·C2H5OH·3H2O (44)和[Sm2Sr2(pydc)5(H2O)9]·2H2O (45)。并研究了它们的荧光性质。
     4.以2,5-吡啶二甲酸为配体，合成了8个锶和锶-过渡金属的杂核配合物：[Sr(pydc)(H2O)]n(46),[CuSr(pydc)2(H2O)4]n(47),[CoSr(pydc)2(H2O)6]2n·H2O (48),[NiSr(pydc)2(H2O)4]n·3nH2O (49),[Sr(H2O)6]n·n[Ni(pydc)2(H2O)2]·2nH2O (50),[NiSr2(pydc)3(H2O)8]n·2nH2O (51),[ZnSr(pydc)2(H2O)5]n(52)[ZnSr2(pydc)3(H2O)10]n·2nH2O (53)。并且研究了配合物47、48和51的磁性，以及配合物46、52和53的荧光性质。
     5.以2,4-吡啶二甲酸为配体，合成了8个含SrII和SrII-MII(M=Co, Ni, Zn, Cu)的杂核配合物：[Sr(pydc)H2O]n(54),[MSr(pydc)2(H2O)2]n(M=Co (55), Ni (56), Zn (57)),[ZnSr(pydc)2(H2O)7]n·4nH2O (58),[SrCu(pydc)2]n(59),[SrCu(pydc)2(H2O)5]n(60)和[Cu3Sr2(pydc)4(Hpydc)2(H2O)2]n(61)。有趣的是，通过改变反应体系的温度，配合物59（三维网状结构）能可逆地转化为配合物60（一维链状结构）。我们研究了配合物54和57的荧光性质和配合物55、56、61的磁性。
     6.以2,3-吡啶二甲酸为配体，合成了五个三维网状的SrII-MII(M=Co, Ni, Zn, Cu)杂核配位聚合物：[MSr(pydc)2(H2O)2]n(M=Co (62), Ni (63)),[MSr2(pydc)3(H2O)4]n·2nH2O (M=Ni (64), Zn(65)),和[CuSr(pydc)2(H2O)3]n·2nH2O (66)。并研究了配合物62和63的磁性。
The coordination complexes supported by nitrogen-containing heterocyclic ligands have attractedintensive attention of coordination chemists due to their fascinating structures and broad applications asfunctional materials in fluorescence, catalysis, adsorption, and magnetism. Among a varieties ofnitrogen-containing heterocyclic compounds, imidazole, pyridine, pyrazole and pyrrole are favorableligands, owing to their variable structures, good biological activity and strong coordination ability. Inthis thesis, we report the synthesis of coordination complexes based on pyridine derivatives, and theirchemical and physical properties. A number of coordination complexes were prepared bymetal-mediated in situ metal/ligand reactions of3-pyridyl-imidazole[1,5-a] pyridine and differentaldehydes. The plausible mechanisms for these in situ metal/ligand reactions were proposed. In addition,a series of AE-Ln (AE=alkaline earth metal; Ln=lanthanide) heteronuclear complexes andAE-transition metal heteronuclear complexes were synthesized by employing four varieties of pyridinedicarboxylic acids as ligands. And their fluorescence and magnetic properties were studied. Theseresults were briefly described as follows:
     1. Under solvothermal conditions, a series of reactions of picolinaldehyde, ammonium acetate, andtransition-metal ions were conducted. Five new ligands,pyridin-2-yl(3-(pyridin-2-yl)imidazo[1,5-a]pyridine-1-yl)methanone (L1),1,2-di(pyridin-2-yl)-1,2-bis[3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl]ethane (L2),1,1’,1’’-(pyridin-2-ylmethanetriyl)-tris{3-(pyridin-2-yl)imidazo[1,5-a]pyridine}(L3),1,1’-(pyridin-2-ylmethylene)bis{3-(pyridin-2-yl)imidazo[1,5-a]pyridine}(L4), and3-(pyridine-2-yl)-1-(pyridin-2-ylmethyl)imidazo[1,5-a]pyridine (L5) and14novel coordinationcomplexes, Fe(L1)Cl2(1), Fe2(L2)Cl4(2), Fe2(L3)Cl4·EtOH (3), Fe(L4)Cl2(4), Co(L1)Cl2·0.5EtOH(5), Co2(L2)Cl4(6), Co2(L3)Cl4·EtOH (7), Co(L5)Cl2(8),[CuI2(L2)Cl2]n(9),[CuII(L3)Cl][CuICl2]·2EtOH (10),[CuIII4(L3)Cl5][Cu2Cl3·2(CuICl2)](11), Cu(L4)Cl·EtOH (12),[L4CuCl]+·[Cu---2Cl3](13),2[HL4CuCl]2+·2(CuCl2)·[CuCl3]2·2H2O (14) were generated via in situmetal-ligand reactions. The structures of these compounds could be controlled rationally via choosingappropriate starting materials and tuning the ratio of the starting materials. The most striking feature ofthe synthesis is that the controllable transformation of the aldehyde group of picolinaldehyde intoketone and secondary, tertiary, and quaternary carbon centers, respectively, has been realized.
     2. The reactions of CuCl2·2H2O (or CuBr2·2H2O),3-(pyridin-2-yl)imidazo[1,5-a]pyridine (HPIP)and formaldehyde, formic acid, N,N-dimethylformamide (DMF) and glyoxal, respectively, in theabsence/presence of acetic acid under solvothermal conditions were investigated. We found that theCuII-mediated multiple coupling of HPIP and formaldehyde, formic acid, DMF and glyoxal, respectively, where the three bonds of formaldehyde, formic acid, DMF and glyoxal were controllablycleaved, was a very efficient strategy for creating the coordination complexes based on the substitutedimidazo[1,5-a]pyridine. Six novel coordination complexes, namely,[L6Cu2Cl2][Cu2Cl4]·2EtOH (15),[L6Cu2Br2][Cu2Br4]·2EtOH (16),[(L7)2Cu3](CuCl2)3·2EtOH (17),2{[(L7)2Cu3](CuBr2)3}·EtOH (18),L8Cu2Cl2(19) and L8Cu2Br2(20)(L6=tetrakis(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methane,L7=tris(3-(pyridin-2-yl)imidazo[1,5-a]pyridin-1-yl)methane, and L8=1,1,2,2-tetrakis(3-(pyridin-2-yl)-imidazo[1,5-a]pyridin-1-yl)ethane), were generated via in situ metal-ligand reactions. And during thestudy of the mechanism of the in situ meta-ligand reactions, four new complexes, namely,[L6Co2Cl4]·2EtOH (21),[Co2(HPIP)2Cl4](22),[Cu2(HPIP)2Cu2Cl4](23) and L9ZnCl2(24) and onenew ligand L9(bis(3-(pyridin-2-yl)imidazo[1,5-a]-pyridin-1-yl)methane) were generated.
     3. The reactions of pyridine-2,6-dicarboxylic acid (H2pydc), lanthanide salts and SrCl2·6H2O (orSr(OH)2·8H2O), result in21new complexes, namely,[Sr3(pydc)2(Hpydc)2(H2O)2]n·2nH2O (25)，[Dy3Sr3(pydc)7(Hpydc)(H2O)9]·6H2O (26)，[Ln2Sr3(pydc)6(H2O)18]·nH2O (Ln=Sm (27), Eu (28), n=11; Gd (29), n=16; Tb (30), Dy (31), n=13)，[LnSr(pydc)3(H2O)5]·Him·H2O (Ln=Sm(32), Eu (33),Gd (34), Tb (35), Dy(36))，[Ln2Sr(pydc)6(H2O)5]·4Him·C2H5OH·nH2O (Ln=Sm(37), n=4; Eu (38), n=5; Gd (39), n=4; Dy(40) n=5)，[LnSr(pydc)3(H2O)4]·Him·3H2O (Ln=Gd (41), Tb (42) Dy (43))，[GdSr(pydc)3(H2O)5]·Him·C2H5OH·3H2O (44)and [Sm2Sr2(pydc)5(H2O)9]·2H2O (45), by employingdifferent amount of imidazole (im) in the reaction system. Their fluorescence properties were studied.
     4. Eight novel SrIIand SrII-transition metal heteronuclear complexes of compositions,[Sr(pydc)(H2O)]n(46),[CuSr(pydc)2(H2O)4]n(47),[CoSr(pydc)2(H2O)6]2n·H2O (48),[NiSr(pydc)2(H2O)4]n·3nH2O (49),[Sr(H2O)6]n·n[Ni(pydc)2(H2O)2]·2nH2O (50),[NiSr2(pydc)3(H2O)8]n·2nH2O (51),[ZnSr(pydc)2(H2O)5]n(52)[ZnSr2(pydc)3(H2O)10]n·2nH2O (53),were afforded by employing pyridine-2,5-dicarboxylic acid as the ligand. The magnetic properties of47，48and51were studied, and the luminescent properties of46，52and53were investigated.
     5. The employment of pyridine-2,4-dicarboxylic acid (H2pydc) in the construction of SrIIandSrII-MII(M=Co, Ni, Zn and Cu) coordination polymers were reported. Eight complexes ofcompositions,[Sr(pydc)H2O]n(54),[MSr(pydc)2(H2O)2]n(M=Co (55), Ni (56), Zn (57)),[ZnSr(pydc)2(H2O)7]n·4nH2O (58),[SrCu(pydc)2]n(59),[SrCu(pydc)2(H2O)5]n(60) and[Cu3Sr2(pydc)4(Hpydc)2(H2O)2]n(61), have been synthesized. Interestingly, complex59(3-D network)can be reversibly transformed into60(1-D chain) by controlling the temperature of the reaction mixture.The luminescent properties of54and57were measured and the magnetic properties of55,56and61were investigated.
     6. Five new3D SrII-MII(M=Co, Ni, Zn, Cu) heterometal coordination polymers based onpyridine-2,3-dicarboxylic acid (H2pydc), namely,[MSr(pydc)2(H2O)2]n(M=Co (62), Ni (63)),[MSr2(pydc)3(H2O)4]n·2nH2O (M=Ni (64), Zn (65)),和[CuSr(pydc)2(H2O)3]n·2nH2O (66) have beensynthesized. The magnetic properties of complexes62and63have been investigated.

引文

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