Zhai Lu, Zhang Wen-Wei, Ren Xiao-Ming, Zuo Jing-Lin
State Key Laboratory of Materials-Oriented Chemical Engineering and College of Science, Nanjing Tech University, Nanjing 210009, P. R. China.
Dalton Trans. 2015 Mar 28;44(12):5746-54. doi: 10.1039/c4dt03794d.
A family of novel lanthanide metal–organic frameworks (MOFs) with formula [Ln2(EBTC)1.5(CH3OH)4]·6H2O [EBTC4− = 1,1′-ethynebenzene-3,3′,5,5′-tetracarboxylate, Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8) and Dy (9)], have been synthesized via solvothermal reaction. All compounds are isostructural, crystallized in the monoclinic space group P21/n, and show a three-dimensional (4,6)-connected network with Schläfli symbol of {310}. Photoluminescent measurements indicated that 1 and 7 emit the luminescence originating from the intraligand π←π* transition, 2 shows the broadband emission due to allowed 4f–5d transitions, and 4–9 show the emission of typical lanthanide f–f transition via the ligand “antenna effect” in the solid state at ambient temperature. Interestingly, compounds 6 and 8 showed microsecond time-scale fluorescence lifetimes with 0.84 ms for 6 and 0.39 ms for 8, respectively. Such unique spectroscopy features may have applications in biomacromolecule research.
通过溶剂热反应合成了一系列通式为[Ln2(EBTC)1.5(CH3OH)4]·6H2O的新型镧系金属有机框架材料（MOF）[EBTC4− = 1,1′-乙炔基苯-3,3′,5,5′-四羧酸酯，Ln = La (1)、Ce (2)、Pr (3)、Nd (4)、Sm (5)、Eu (6)、Gd (7)、Tb (8) 和 Dy (9)]。所有化合物均为同构体，结晶于单斜空间群P21/n，呈现出三维（4,6）连接网络，其Schläfli符号为{310}。光致发光测量表明，1和7发出源于配体内π←π*跃迁的发光，2由于允许的4f–5d跃迁而呈现宽带发射，4 - 9在室温下的固态中通过配体“天线效应”呈现典型的镧系f–f跃迁发射。有趣的是，化合物6和8表现出微秒级的荧光寿命，6为0.84 ms，8为0.39 ms。这种独特的光谱特征可能在生物大分子研究中具有应用价值。
