Department of Chemistry and Biochemistry , University of South Carolina , Columbia , South Carolina 29208 , United States.
Center for Hierarchical Wasteform Materials , Columbia , South Carolina 29208 , United States.
Inorg Chem. 2018 Sep 17;57(18):11606-11615. doi: 10.1021/acs.inorgchem.8b01729. Epub 2018 Sep 5.
Single crystals of 13 new uranyl germanate salt-inclusion materials were grown from alkali halide fluxes: [CsCsF][(UO)(GeO)] (1), [CsAgCl][(UO)(GeO)] (2), [CsAgNaCl][(UO)(GeO)] (3), [CsAgNaCl][(UO)(GeO)] (4), [CsKCl][(UO)(GeO)] (5), [CsKAgCl][(UO)(GeO)] (6), [KKCl][(UO)(GeO)] (7), [KKBrF][(UO)(GeO)] (8), [NaRbF][(UO)(GeO)] (9), [KNaKCsClF][(UO)(GeO)] (10), [KNaKCsClF][(UO)(GeO)] (11), [KKCsF][(UO)(GeO)] (12), and [CsCsCl][(UO)O(GeO)] (13). Structures 1-12 contain the same [(UO)(GeO)] framework whose pores are filled with varied salt species selected by the choice of the specific alkali halide flux used for crystal growth. The size and identity of the salt species also influence whether the [(UO)(GeO)] framework adopts a monoclinic or orthorhombic symmetry. The 13th composition, [CsCsCl][(UO)O(GeO)] (13), crystallizes in a new structure type in the hexagonal crystal system and contains large channels. Optical characterization was performed on [CsKAgCl][(UO)(GeO)] (6) and [KKCsF][(UO)(GeO)] (12), and both exhibit UV-vis absorption and luminescence typical of the uranyl group. The fluorine-containing composition luminesces 10 times as intensely as does the chlorine-containing composition.
从碱金属卤化物熔剂中生长出 13 种新的铀锗酸盐盐包合物单晶：[CsCsF][(UO)(GeO)]（1）、[CsAgCl][(UO)(GeO)]（2）、[CsAgNaCl][(UO)(GeO)]（3）、[CsAgNaCl][(UO)(GeO)]（4）、[CsKCl][(UO)(GeO)]（5）、[CsKAgCl][(UO)(GeO)]（6）、[KKCl][(UO)(GeO)]（7）、[KKBrF][(UO)(GeO)]（8）、[NaRbF][(UO)(GeO)]（9）、[KNaKCsClF][(UO)(GeO)]（10）、[KNaKCsClF][(UO)(GeO)]（11）、[KKCsF][(UO)(GeO)]（12）和[CsCsCl][(UO)O(GeO)]（13）。结构 1-12 包含相同的[(UO)(GeO)]框架，其孔被通过选择用于晶体生长的特定碱金属卤化物熔剂而选择的不同盐物种填充。盐物种的尺寸和身份也会影响[(UO)(GeO)]框架采用单斜还是正交对称。第 13 个组成部分[CsCsCl][(UO)O(GeO)]（13）在六方晶系中结晶为新的结构类型，并包含大通道。对[CsKAgCl][(UO)(GeO)]（6）和[KKCsF][(UO)(GeO)]（12）进行了光学特性研究，两者都表现出典型的铀酰基团的紫外-可见吸收和发光。含氟的组成部分的发光强度是含氯组成部分的 10 倍。
