Wang Zhong-Xia, Wang Ai-Ling, Wei Xiao-Yan, Qu Yan-Rong, Yue Bin, Kang Jie, Chu Hai-Bin, Zhao Yong-Liang
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, People's Republic of China.
Luminescence. 2015 Sep;30(6):835-41. doi: 10.1002/bio.2829. Epub 2015 Jan 13.
Two complexes of Tb(3+), Gd(3+) /Tb(3+) and one heteronuclear crystal Gd(3+)/Tb(3+) with phenoxyacetic acid (HPOA) and 2,4,6-tris-(2-pyridyl)-s-triazine (TPTZ) have been synthesized. Elemental analysis, rare earth coordination titration, inductively coupled plasma atomic emission spectrometry (ICP-AES) and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) analysis show that the two complexes are Tb2 (POA)6 (TPTZ)2 · 6H2O and TbGd(POA)6 (TPTZ)2 · 6H2O, respectively. The crystal structure of TbGd(POA)6 (TPTZ)2 · 2CH3OH was determined using single-crystal X-ray diffraction. The monocrystal belongs to the triclinic system with the P-1 space group. In particular, each metal ion is coordinately bonded to three nitrogen atoms of one TPTZ and seven oxygen atoms of three phenoxyacetic ions. Furthermore, there exist two coordinate forms between C6H5OCH2COO(-) and the metal ions in the crystal. One is a chelating bidentate, the other is chelating and bridge coordinating. Fluorescence determination shows that the two complexes possess strong fluorescence emissions. Furthermore, the fluorescence intensity of the Gd(3+)/Tb(3+) complex is much stronger than that of the undoped complex, which may result from a decrease in the concentration quench of Tb(3+) ions, and intramolecular energy transfer from the ligands coordinated with Gd(3+) ions to Tb(3+) ions.
合成了铽(Tb(3+))、钆(Gd(3+))/铽(Tb(3+))的两种配合物以及一种钆(Gd(3+)/Tb(3+))与苯氧乙酸(HPOA)和2,4,6-三(2-吡啶基)-s-三嗪(TPTZ)的异核晶体。元素分析、稀土配位滴定、电感耦合等离子体原子发射光谱法(ICP-AES)和热重分析-差示扫描量热法(TG-DSC)分析表明,这两种配合物分别为Tb2 (POA)6 (TPTZ)2 · 6H2O和TbGd(POA)6 (TPTZ)2 · 6H2O。使用单晶X射线衍射确定了TbGd(POA)6 (TPTZ)2 · 2CH3OH的晶体结构。该单晶属于三斜晶系,空间群为P-1。特别地,每个金属离子与一个TPTZ的三个氮原子以及三个苯氧乙酸离子的七个氧原子配位键合。此外,晶体中C6H5OCH2COO(-)与金属离子之间存在两种配位形式。一种是螯合双齿配位,另一种是螯合和桥连配位。荧光测定表明,这两种配合物具有强烈的荧光发射。此外,Gd(3+)/Tb(3+)配合物的荧光强度比未掺杂的配合物强得多,这可能是由于Tb(3+)离子浓度猝灭的降低以及从与Gd(3+)离子配位的配体到Tb(3+)离子的分子内能量转移所致。