【作者】 迟玉贤；

【导师】 牛淑云；

【作者基本信息】 辽宁师范大学 ， 物理化学， 2008， 博士

【摘要】 本文采用水热,恒温磁力搅拌,振荡以及微波辐射等合成方法,以镧系离子和具有d¹⁰价电子构型的Cd²⁺和Zn²⁺为中心金属,选择具有羧酸基官能团的有机共轭体系为主要配体,合成了未见报道的27种化合物。培养出了单晶体,通过X-光单晶衍射确定了它们的晶体结构。包括6种Cd-Ln配合物,Ln=Sm,Dy,Yb,Pr,Nd（2种）;9种Zn-Ln配合物,Ln=Nd,Pr,Sm,Eu,Tb,Ho（2种）,Dy（2种）;6种Ln-Ln配合物,Ln=Er,Yb（2种）,Ho（3种）;6种d¹⁰金属配合物,Zn（2种）,Cd（4种）。对全部化合物进行了IR光谱,UV-Vis-NIR吸收光谱以及可见和近红外激发和发射光谱测试,并进行了较详尽的对比分析和指认。重点研究了化合物的发光性能,得到以下结果:（1）4d-4f（Cd-Ln）配合物:Cd-Ln配合物合成很难。本文合成了6种Cd-Ln配合物,它们均具有良好的发光性能。特别是在近红外区的发光具有特殊性;得到了一些与理论值及文献报道相比较有明显差异的发射光谱,即Ln³⁺的特征f-f发射带产生了明显的位移、加宽或劈裂。这是由于在4d-4f配合物中,Cd…Ln距离较近（3.6706～3.950（?））,不但促进了d→f能量有效传递,保证了d-块对f-块发光的敏化。而且由于Cd²⁺的4d轨道和Ln³⁺的4f轨道相互作用,使体系内部的能级发生调节,最终使发射谱带产生明显的位移、加宽或劈裂。这一点,正可以被利用来设计组装新型d-f配合物,让4d和4f轨道相互作用,从而使体系内部能级受到调谐,借此可能得到具有特殊发光波长的发光配合物或材料。（2）3d-4f（Zn-Ln）配合物具有无限结构的Zn-Ln配合物的报道并不多,并且已报道的这类化合物多以席夫碱为配体。本文采用2,5-吡啶二羧酸和均四苯甲酸为主要配体,合成了6种具有1D链状结构的Zn-Ln配聚物和1种具有2D无限结构的Zn-Dy配聚物。它们均具有较良好的发光性能,并且d-块（Zn-L部分）对Ln³⁺的发光也起到一定的敏化作用。（3）对化合物的发光性能进行了详尽的对比、分析,并进行了全面的指认。特别是对一些与理论值和文献报道值有差异的发光谱带,是我们首次采用将化合物的电子吸收光谱与发射光谱相关联的理论方法进行对比和解析,同时又将化合物结构与光谱相关联,来解释所产生的发射谱带的位移、加宽和劈裂现象。得到了圆满的答案。（4）首次合成了可以在近红外发光的Sm-Cd和Sm-Zn杂核配合物,并对其进行了较详尽的分析。以上工作,特别是关于d-f配合物的研制及发光性能的研究,可为获得发光效率高、发光波长可比较自由调谐的新型发光材料,尤其是近红外发光材料,提供重要的启发和新方法。更多还原

【Abstract】 We synthesized twenty-seven new complexes by the hydrothermal,magnetic stirring,vibrating and microwave methods.In which,the lanthanide ions and the d¹⁰ (Zn²⁺ and Cd²⁺) ions were selected as the central metal ions,and the organic conjugated systems with carboxylate group were chosen as the main ligands.The single-crystal of these complexes was obtained and their structures were determined by the single-crystal X-ray diffraction.There includes six Cd-Ln complexes,Ln=Sm, Dy,Yb,Pr,Nd（two complexes）;nine Zn-Ln complexes,Ln=Nd,Pr,Sm,Eu,Tb,Ho （two complexes）,Dy（two complexes）;six Ln-Ln complexes,Ln=Er,Yb（two complexes）,Ho（three complexes）;and six d¹⁰ metal complexes,Zn（two complexes） and Cd（four complexes）.The IR and UV-Vis-NIR absorption spectra,excitation and emission spectra in the visible and near-infrared（NIR） region were determined,and analyzed with detail.The study of the luminescent properties of complexes was the emphases and the following results were summarized:（1） 4d-4f（Cd-Ln） coordination complexes:The Cd-Ln complexes are very difficult to be synthesized.Six Cd-Ln coordination complexes were obtained and they have excellent luminescent properties. Especially in the NIR region,the luminescent properties are special:the emission spectra have difference from the theoretical values and some reported complexes,that is,the characteristic f-f emission bands of Ln³⁺ ions present obvious shifts,broad and splittings.In the 4d-4f complexes,the Cd…Ln separation（3.6706～3.950（?）） is smaller. This is more feasible for the efficient d→f energy transfer and guarantees the sensitization of the d-block component to the f-block component.In addition,the interaction between the 4d orbitals of the Cd²⁺ ion and the 4f orbitals of the Ln³⁺ ion causes the intramolecular levels to be adjusted,which causes the emission bands to present shifts,broad and splittings.Maybe we can use it to design new d-f coordination complexes,in which the interaction between 4d orbitals and 4f orbitals cause the intramolecular levels to be adjusted.So we can obtain novel luminescent coordination complexes or materials with special emission bands. （2） 3d-4f（Zn-Ln） coordination complexesThe reports about Zn-Ln coordination complexes with unlimited structure are not many,and most of them use the shiff-base ligands.We select the pyridine-2,5-dicarboxylic acid and benzene-1,2,4,5-tetracarboxylic acid as ligands and synthesize six Zn-Ln coordination polymers with 1D chain structure and one Zn-Ln coordination polymer with 2D structure.They have good luminescent properties,and the d-block component（Zn-L section） can also sensitize the luminescence of Ln³⁺ ions.（3） The luminescent properties of the complexes are comparatively analyzed and assigned with detail.For the emission bands which have difference from the theoretical values or some reports,we first illustrate the shifts,broad and splittings of emission bands by the method of comparing and analyzing the relationship between the absorption spectra and the emission spectra,as well as the connection between the structure and the spectra.The satisfying results were received.（4） The Sm-Cd（1） and Sm-Zn（9） hetetronuclear complexes with NIR luminescent properties were first synthesized,and they were analyzed in detail.All the above works,the study of the d-f coordination complexes in particular, can provide important enlightenment and a new way to obtain a new type of luminescent material,especially in the NIR region,which has high efficiency and has the adjustable luminescent wavelength in relative free.更多还原