首页|4'-(2-吡啶基)三联吡啶的镧系(Ⅲ)配合物的晶体结构、荧光性质和磁性

4'-(2-吡啶基)三联吡啶的镧系(Ⅲ)配合物的晶体结构、荧光性质和磁性

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以4'-(2-吡啶基)-2,2':6',2"-三联吡啶(2-pyterpy)为配体,通过溶剂热法合成了 5个双核配合物[Ln(2-pyterpy)(NO3)2(μ-OCH3)]2(Ln-2-pyterpy,Ln=Pr、Sm、Eu、Dy、Er)。单晶 X 射线衍射分析表明,配合物 Pr-2-pyterpy 和 Sm-2-pyterpy 同构,属于单斜晶系,P21空间群,a=0。956 43(19)nm,b=1。965 4(4)nm,c=1。193 5(2)nm,β=90。41(3)°。配合物Er-2-pyterpy 属于单斜晶系,C2/c空间群,a=2。838 8(6)nm,b=1。204 8(2)nm,c=1。520 6(3)nm,β=121。70(3)°。粉末X射线衍射研究表明,配合物 Eu-2-pyterpy 与 Dy-2-pyterpy同构且与文献报道的配合物[Ln(2-pyterpy)(NO3)2(μ-OCH3)]2(Ln=Tb,Dy)结构相同,属于单斜晶系,P21/n空间群。镧系收缩效应在调整该系列配合物结构中起到了重要作用。固态配合物Ln-2-pyterpy(Ln=Pr、Sm、Eu、Dy)均发射Ln(Ⅲ)的特征荧光。在300 K,配合物Ln-2-pyterpy(Ln=Pr、Sm、Eu、Dy)的xMT实验值与2个孤立的Ln(Ⅲ)离子的理论值基本一致。根据2 K时xMT实验值推断,配合物Sm-2-pyterpy和Eu-2-pyterpy的顺磁离子间分别通过甲氧基桥传递弱的反铁磁和铁磁耦合作用。
Lanthanide(Ⅲ)complexes derived from 4'-(2-pyridyl)-2,2':6',2"-terpyridine:Crystal structures,fluorescent and magnetic properties
Five dinuclear complexes[Ln(2-pyterpy)(NO3)2(μ-OCH3)]2(Ln-2-pyterpy,Ln=Pr,Sm,Eu,Dy,Er)were synthesized by solvothermal method using 4'-(2-pyridyl)-2,2':6',2"-terpyridine(2-pyterpy)as ligand.Single crystal X-ray diffraction analysis showed that complexes Pr-2-pyterpy and Sm-2-pyterpy are isomorphic and crystallize in monoclinic system,space group P2,with a=0.956 43(19)nm,b=1.965 4(4)nm,c=1.193 5(2)nm,β=90.41(3)°.Com-plex Er-2-pyterpy crystallizes in monoclinic system,space group C2/c with a=2.838 8(6)nm,b=1.204 8(2)nm,c=1.520 6(3)nm,β=121.70(3)°.Powder X-ray diffraction results showed that complexes Ln-2-pyterpy(Ln=Eu,Dy)are isomorphic and have the same structure as the reported complexes[Ln(2-pyterpy)(NO3)2(µ-OCH3)]2(Ln=Tb,Dy),crystallizing in monoclinic crystal system,space group P21/n.The lanthanide contraction effect plays an important role in adjusting the structure of this series of complexes.The solid complexes Ln-2-pyterpy(Ln=Pr,Sm,Eu,Dy)emitted the characteristic fluorescence of Ln(Ⅲ)ions.At 300 K,the xMT experimental values of complexes Ln-2-py-terpy(Ln=Pr,Sm,Eu,Dy)were consistent with the theoretical values of two corresponding isolated Ln(Ⅲ)ions.Ac-cording to the xMT experimental value at 2 K,the weak antiferromagnetic and ferromagnetic coupling effects be-tween the Ln(Ⅲ)ions of the complexes Sm-2-pyterpy and Eu-2-pyterpy are transmitted by methoxy-bridge,respec-tively.CCDC:2333490,Pr-2-pyterpy;2333491,Sm-2-pyterpy;2333483,Er-2-pyterpy.

lanthanide(Ⅲ)complexterpyridinefluorescent propertymagnetic property

王朝阳、杨春、宋瑶瑶、韩娜、刘晓蒙、王庆伦

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河北工业大学化工学院,天津市本质安全化工技术重点实验室,天津 300130

南开大学化学学院,先进能源材料化学教育部重点实验室,天津 300071

镧系(Ⅲ)配合物 三联吡啶 荧光性质 磁性

国家自然科学基金国家自然科学基金国家自然科学基金河北省引进留学人员资助项目

217711112110109621371104C20200317

2024

无机化学学报
中国化学会

无机化学学报

CSTPCD北大核心
影响因子:0.665
ISSN:1001-4861
年,卷(期):2024.40(8)