二茂铁苯甲酸类稀土配合物的合成、表征及性能研究
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摘要
本文利用邻二茂铁基苯甲酸钠(o-NaOOCH_4C_6Fc)和邻二茂铁甲酰基苯甲酸钠(o-NaOOCH_4C_6OCFc)(Fc=(η~5-C5H5)Fe(η~5-C5H5))两种二茂铁苯甲酸类化合物为配体,与水合氯化稀土LnCl3·6H2O通过分子自组装,制备出两个系列的稀土配合物,即,{[Ln(OOCH_4C_6Fc)_4(H_2O)_2](H3O)}n (Ln = La(1), Pr(2), Sm(3), Eu(4), Gd(5), Tb(6), Er(7), Lu(8))和{[Ln(OOCH_4C_6OCFc)4(H2O)2](H3O)}n (Ln = La(9), Pr(10), Sm(11), Eu(12), Gd(13), Tb(14), Er(15), Lu(16))。通过红外光谱、紫外光谱、元素分析、差热热重等对配合物进行了分析。参考相关文献推测其结构,其中稀土离子都是与八个氧原子配位的,1-8中两个来自配位的水分子,两个来自单齿配位的FcC6H4COO-,四个来自双齿桥联的μ2-η~2--OOCH_4C_6Fc;9-16中两个来自配位的水分子,两个来自单齿配位的FcCOC6H4COO- ,四个来自双齿桥联的μ2-η~2--OOCH_4C_6OCFc。
同时,以THF为溶剂对配合物1-8和9-16进行了荧光测试,结果表明它们都是配体之间的电荷转移所产生的荧光。配合物1-16在DMF溶液中的摩尔电导率研究表明这些配合物为弱电解质物质。
Two series of ferrocene benzonitrile acids lanthanide(III) complexes, namely, {[Ln(OOCH_4C_6Fc)_4(H_2O)_2](H3O)}n (Ln = La(1), Pr(2), Sm(3), Eu(4), Gd(5), Tb(6), Er(7), Lu(8))and {[Ln(OOCH_4C_6OCFc)4(H2O)2](H3O)}n (Ln = La(9), Pr(10), Sm(11), Eu(12), Gd(13), Tb(14), Er(15), Lu(16)), were obtained by treating o-ferrocenyl- benzoate(o-NaOOCH_4C_6Fc) and o-ferrocencarbonylbenzoate(o-NaOOCH_4C_6OCFc) (Fc=(η~5-C5H5)Fe(η~5-C5H5)) with LnCl3·6H2O. These complexes were characterized by infrared spectrum, ultra-violet spectrograph, element analysis and thermogravimetry analysis. On the basis of spectroscopical analysis and known analogous, their composition and structures are proposed. Each Ln(III) ion is coordinated by eight oxygen atoms from two terminal monodentate coordinated FcC6H4COO- units or FcCOC6H4COO- units, two terminal monodentate coordinated H2O molecules, and fourμ2-η~2--OOCH_4C_6Fc units orμ2-η~2--OOCH_4C_6OCFc units.
Fluorescent spectra of complexes 1-8 and 9-16 using liquid sample suggest that, finally they all exhibita a broad emission, the emissions of 1-16 can be attributed to the ligand charge transfer. Molar conductivity of these complexes indicates that they are weak electrolyte
同时,以THF为溶剂对配合物1-8和9-16进行了荧光测试,结果表明它们都是配体之间的电荷转移所产生的荧光。配合物1-16在DMF溶液中的摩尔电导率研究表明这些配合物为弱电解质物质。
Two series of ferrocene benzonitrile acids lanthanide(III) complexes, namely, {[Ln(OOCH_4C_6Fc)_4(H_2O)_2](H3O)}n (Ln = La(1), Pr(2), Sm(3), Eu(4), Gd(5), Tb(6), Er(7), Lu(8))and {[Ln(OOCH_4C_6OCFc)4(H2O)2](H3O)}n (Ln = La(9), Pr(10), Sm(11), Eu(12), Gd(13), Tb(14), Er(15), Lu(16)), were obtained by treating o-ferrocenyl- benzoate(o-NaOOCH_4C_6Fc) and o-ferrocencarbonylbenzoate(o-NaOOCH_4C_6OCFc) (Fc=(η~5-C5H5)Fe(η~5-C5H5)) with LnCl3·6H2O. These complexes were characterized by infrared spectrum, ultra-violet spectrograph, element analysis and thermogravimetry analysis. On the basis of spectroscopical analysis and known analogous, their composition and structures are proposed. Each Ln(III) ion is coordinated by eight oxygen atoms from two terminal monodentate coordinated FcC6H4COO- units or FcCOC6H4COO- units, two terminal monodentate coordinated H2O molecules, and fourμ2-η~2--OOCH_4C_6Fc units orμ2-η~2--OOCH_4C_6OCFc units.
Fluorescent spectra of complexes 1-8 and 9-16 using liquid sample suggest that, finally they all exhibita a broad emission, the emissions of 1-16 can be attributed to the ligand charge transfer. Molar conductivity of these complexes indicates that they are weak electrolyte
引文
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