Lanthanide Germanate Cluster Organic Frameworks Based on {Ln8Ge12} Clusters: From One-Dimensional Chains to Two-Dimensional Layers and Three-Dimensional Frameworks

详细信息    查看全文

• 作者：Lei-Lei Li ; Gao-Juan Cao ; Jun-Wei Zhao ; Huan He ; Bai-Feng Yang ; Guo-Yu Yang
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：June 6, 2016
• 年：2016
• 卷：55
• 期：11
• 页码：5671-5683
• 全文大小：740K
• 年卷期：0
• ISSN：1520-510X

文摘

Under hydrothermal conditions, six series of novel lanthanide (Ln) organogermanates (LnGs) [Ln₈Ge₁₂(μ₃-O)₂₄E₁₂(H₂O)₁₆]·14H₂O (Ln³⁺ = Pr³⁺, 1; Nd³⁺, 2; Sm³⁺, 3; Eu³⁺, 4; Gd³⁺, 5; one-dimensional (1-D) LnG cluster organic chain (LnGCOC)), {[Nd₈Ge₁₂(μ₃-O)₂₄E₁₂(H₂O)₁₀](μ₂-H₂O)₂[Nd₈Ge₁₂(μ₃-O)₂₄E₁₂(H₂O)₁₆]}·18H₂O (6, two-dimensional (2-D) planar LnG cluster organic layer (LnGCOL)), {[Ln₂GeE(HO)₂O(H₂O)(CH₃COO)₂(CO₃)]₂[Ln₈Ge₁₂E₁₂(μ₃-O)₂₄(H₂O)₁₀]}·6H₂O (Ln³⁺ = Pr³⁺, 7; Nd³⁺, 8; 2-D wave-shaped LnGCOL), [TbGeE(HO)₂O(H₂O)(pca)]₂[Tb₈Ge₁₂E₁₂(μ₃-O)₂₄(H₂O)₈]·10H₂O (9, three-dimensional (3-D) LnG cluster organic framework (LnGCOF)), {([Nd(pza)₂(H₂O)₂]₂[Nd₈Ge₁₂E₁₂(μ₃-O)₂₄(H₂O)₁₂])([Nd(pza)₂]₂[Nd₈Ge₁₂E₁₂(Hpza)₂(μ₃-O)₂₄(H₂O)₁₀])}·4OH·14H₂O (10, 3-D LnGCOF), {[Nd₈Ge₁₂E₁₂(μ₃-O)₂₄(H₂O)₁₀][Nd(pca)(pda)(H₂O)]₂}·12H₂O (11, 3-D LnGCOF) and {[Nd₈Ge₁₂E₁₂(μ₃-O)₂₄(H₂O)₁₀][Nd(pza)(pda)(H₂O)]₂}·12H₂O (12, 3-D LnGCOF) (Hpca = 2-picolinic acid, H₂pda = 2,6-pyridinedicarboxylic acid, Hpza = 2-pyrazinecarboxylic acid) were prepared by introducing the second auxiliary ligands into the organogermanate–lanthanide–oxide reaction system. The obtainment of these LnGs realized the utilization of the second auxiliary ligands inducing the assembly from 1-D LnGCOCs to 2-D LnGCOLs and 3-D LnGCOFs based on LnG cluster (LnGC) {Ln₈Ge₁₂E₁₂(μ₃-O)₂₄(H₂O)₁₆}({Ln₈Ge₁₂}) units and Ln–organic complexes or organic ligand connectors. It should be noted that the well-organized structural constructions of 1–12 can be visualized as the gradual replacement of active water sites located at equatorial and polar positions on the hypothetical [Ln₈Ge₁₂(μ₃-O)₂₄E₁₂(H₂O)₁₈] LnGC core with oxygen or nitrogen atoms from organic ligands. The solid-state luminescent properties of 2, 3, 4, 6, and 8–12 have been investigated at room temperature.