Li Lei-Lei, Pan Rui, Zhao Jun-Wei, Yang Bai-Feng, Yang Guo-Yu
MOE Key Laboratory of Cluster Science, School of Chemistry, Beijing Institute of Technology, Beijing 100081, China.
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, China.
Dalton Trans. 2016 Jul 26;45(30):11958-67. doi: 10.1039/c6dt01629d.
Six new lanthanide (Ln) germanate cluster organic frameworks (LnGeCOFs) derived from {Ln8Ge12} cage cluster units {[Nd(pza)2(H2O)] [Nd8Ge12(μ3-O)24E12(pza)(H2O)12]}·3H2O (1), {[Dy(CH3COO)(CO3)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)12]}·11H2O (2), {[TbGeE(HO)2O(pza) (H2O)]2[Tb8Ge12(μ3-O)24E12(H2O)6]}·18H2O (3), {[DyGeE(HO)2O(C3H5NO2)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)8]}·8H2O (4), {[Tb(pca)2 (H2O)]3[Tb8Ge12(μ3-O)24E12(H2O)4]}·(OH)3·10H2O (5) and {[Dy(pza)2(H2O)][Dy(pza)2(H2O)2][Dy(pza)3(H2O)][Dy8Ge12(μ3-O)24E12(pza)(HCOO) (H2O)6]}·5H2O (6) have been hydrothermally synthesized and structurally characterized. Increasing the amount of the second ligands can induce not only the assembly from 1 to 5, 6 based on Ln oxides as the starting sources, but also the assembly from 2 to 3, 4 based on Ln salts as the starting sources. The successful preparation of these LnGeCOFs suggests the importance of the second ligands in the structural construction of 1-6. To our knowledge, 1 is the first example that includes right- and left-handed helical chains among LnGeCOFs based on bis(carboxyethylgermanium)sesquioxide. 2, 4 and 6 are the first dysprosium incorporated organogermanates based on bis(carboxyethylgermanium)sesquioxide. 4 and 5 display very open framework structures with a solvent-accessible volume of 34.6% for 4 and 35.0% for 5. Moreover, the solid-state photoluminescence properties of 1, 3 and 5 have been investigated at room temperature and they exhibit the characteristic emission bands derived from Ln cations.
六种新型镧系锗酸盐簇有机框架（LnGeCOFs），它们源自{Ln8Ge12}笼簇单元{[Nd(pza)2(H2O)] [Nd8Ge12(μ3-O)24E12(pza)(H2O)12]}·3H2O（1）、{[Dy(CH3COO)(CO3)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)12]}·11H2O（2）、{[TbGeE(HO)2O(pza) (H2O)]2[Tb8Ge12(μ3-O)24E12(H2O)6]}·18H2O（3）、{[DyGeE(HO)2O(C3H5NO2)(H2O)]2[Dy8Ge12(μ3-O)24E12(H2O)8]}·8H2O（4）、{[Tb(pca)2 (H2O)]3[Tb8Ge12(μ3-O)24E12(H2O)4]}·(OH)3·10H2O（5）和{[Dy(pza)2(H2O)][Dy(pza)2(H2O)2][Dy(pza)3(H2O)][Dy8Ge12(μ3-O)24E12(pza)(HCOO) (H2O)6]}·5H2O（6）已通过水热法合成并进行了结构表征。增加第二配体的量不仅可以诱导以Ln氧化物为起始原料从1组装成5、6，还可以诱导以Ln盐为起始原料从2组装成3、4。这些LnGeCOFs的成功制备表明第二配体在1 - 6结构构建中的重要性。据我们所知，1是基于双（羧乙基锗）倍半氧化物的LnGeCOFs中第一个包含右手和左手螺旋链的例子。2、4和6是基于双（羧乙基锗）倍半氧化物的第一个掺入镝的有机锗酸盐。4和5显示出非常开放的框架结构，4的溶剂可及体积为34.6%，5的为35.0%。此外，已在室温下研究了1、3和5的固态光致发光性质，它们表现出源自Ln阳离子的特征发射带。
