Ji Huanyao, Li Xiaomin, Xu Donghua, Zhou Yunshan, Zhang Lijuan, Zuhra Zareen, Yang Shaowei
State Key Laboratory of Chemical Resource Engineering, Institute of Science, Beijing University of Chemical Technology , Beijing 100029, P. R. China.
Inorg Chem. 2017 Jan 3;56(1):156-166. doi: 10.1021/acs.inorgchem.6b01852. Epub 2016 Dec 12.
A series of isostructural compounds Na(HL)(CHCOO)Ln(Al(OH)MoO)(HO)·10HO [L = nicotinate; Ln = Eu (1), Tb (2)] and Na(HL)(CHCOO)EuTbLa(AlMo(OH)O)(HO)·10HO (3-8, L = nicotinate), wherein Anderson-type polyanions AlMo(OH)O as basic inorganic building blocks are connected by Eu(CHCOO)(HL)(HO)] and [Na(HO)] cations, resulting in formation of three-dimensional lanthanide metal-organic open frameworks, were synthesized successfully with AlCl·6HO, NaMoO·2HO, nicotinic acid, and lanthanide nitrates as starting materials. The compounds were characterized by UV-vis, IR, elemental analysis, powder XRD, and TG-DTA measurements. The single-crystal structures of compounds 1 and 2 show that the two compounds display three-dimensional open frameworks with 1D channels along the b and c axes. Investigation of the energy transfer mechanism indicated that the organic nicotinate ligand can transfer energy efficiently to Tb rather than Eu. The influence of the POM moiety on the fluorescence of the compounds is also studied. Compounds 1-8 exhibit tunable luminescence color, and emitting of white light was realized through adjusting the molar ratio of Eu:Tb:La within the compounds.
一系列同构化合物Na(HL)(CH₃COO)Ln(Al(OH)MoO₄)(H₂O)·10H₂O [L = 烟酸酯；Ln = Eu (1)，Tb (2)] 以及Na(HL)(CH₃COO)EuₓTbᵧLa₁₋ₓ₋ᵧ(AlMo₄(OH)₉O₁₂)(H₂O)·10H₂O (3 - 8, L = 烟酸酯)，其中作为基本无机结构单元的安德森型聚阴离子AlMo₄(OH)₉O₁₂通过Eu(CH₃COO)₃(HL)(H₂O)]和[Na(H₂O)]⁺阳离子相连，从而形成三维镧系金属有机开放框架，以AlCl₃·6H₂O、Na₂MoO₄·2H₂O、烟酸和镧系硝酸盐为起始原料成功合成。通过紫外可见光谱、红外光谱、元素分析、粉末X射线衍射和热重 - 差示热分析测量对这些化合物进行了表征。化合物1和2的单晶结构表明，这两种化合物呈现出沿b轴和c轴具有一维通道的三维开放框架。对能量转移机制的研究表明，有机烟酸酯配体能够有效地将能量转移给Tb而非Eu。还研究了多金属氧酸盐部分对化合物荧光的影响。化合物1 - 8表现出可调谐的发光颜色，并且通过调节化合物中Eu:Tb:La的摩尔比实现了白光发射。
