College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China.
J Fluoresc. 2010 May;20(3):763-70. doi: 10.1007/s10895-010-0619-z. Epub 2010 Mar 3.
The complex of Tb(TPTZ)Cl(3).3H(2)O was synthesized by adding the ethyl alcohol solution of TbCl(3) (1 mmol) to the solution of 2,4,6-tris-(2-pyridyl)-s-triazine(TPTZ, 1 mmol) with constant stirring. The solution which had been filtered was kept at the room temperature for 4 weeks, and then a kind of transparent crystal was formed. Besides, nine kinds of solid complexes in the different molar proportion of terbium to gadolinium had been synthesized by adopting the similar method mentioned above. It was inferred from the elemental analysis and rare earth complexometry that the composition of these complexes is (Tb(x)Gd(y))(TPTZ)Cl(3).3H(2)O (x : y = 0.9 : 0.1, 0.8 : 0.2, 0.7 : 0.3, 0.6 : 0.4, 0.5 : 0.5, 0.4 : 0.6, 0.3 : 0.7, 0.2 : 0.8, 0.1 : 0.9). The absorption spectra and photoluminescence of the complexes were determined in dimethylsulfoxide (DMF), which showed that the excitation of the complexes is mostly ligand based. The triplet state energy level of TPTZ was measured, indicating that the lowest excitation state energy level of Tb(III) and the triplet state energy level of TPTZ match well each other. The fluorescent data indicated that the fluorescent emission intensity of Tb(3+) ions would be enhanced in the complexes after terbium was doped with Gd(3+) ion. When x : y was 0.5 : 0.5, the fluorescent emission intensity was the largest. The result obtained by testing the X-ray diffraction of the monocrystal revealed that the molecular formula of the mono-crystal complex is [Tb(TPTZ)(H(2)O)(6)]Cl(3).3H(2)O. The number of metal ion coordinates is nine, and the tridentate TPTZ and six water molecules are bonded with terbium respectively. Besides, it also revealed that the monocrystal belongs to the monoclinic system, and space group Cc with the following unit cell parameters is a = 1.4785 (3) nm, b = 1.0547 (2) nm, c = 1.7385 (4) nm, beta = 94.42 (3) degrees, V = 2.7028 (9) nm(3) and Z = 4.
三氯化三(2,4,6-三吡啶基)合铽配合物的合成方法是:将 TbCl3(1mmol)的乙醇溶液加入到 2,4,6-三(2-吡啶基)均三嗪(TPTZ,1mmol)的溶液中,搅拌均匀。过滤溶液,在室温下放置 4 周,然后形成一种透明晶体。此外,通过采用类似的方法合成了九种不同摩尔比的铽镝固体配合物。通过元素分析和稀土络合滴定法推断这些配合物的组成是(Tb(x)Gd(y))(TPTZ)Cl3.3H2O(x:y=0.9:0.1、0.8:0.2、0.7:0.3、0.6:0.4、0.5:0.5、0.4:0.6、0.3:0.7、0.2:0.8、0.1:0.9)。配合物的吸收光谱和光致发光在二甲基亚砜(DMF)中进行了测定,结果表明配合物的激发主要是配体基。测定了 TPTZ 的三重态能级,表明 Tb(III)的最低激发态能级与 TPTZ 的三重态能级相匹配。荧光数据表明,铽掺杂镝后,配合物中 Tb(3+)离子的荧光发射强度增强。当 x:y 为 0.5:0.5 时,荧光发射强度最大。单晶 X 射线衍射测试结果表明,单晶配合物的分子式为[Tb(TPTZ)(H2O)(6)]Cl3.3H2O。金属离子配位数为 9,三齿 TPTZ 和六水分子分别与铽键合。此外,还表明单晶属于单斜晶系,空间群 Cc,以下单元胞参数为:a=1.4785(3)nm,b=1.0547(2)nm,c=1.7385(4)nm,β=94.42(3)°,V=2.7028(9)nm3 和 Z=4。