当前位置: X-MOL 学术Inorg. Chem. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Leveraging Nitrogen Linkages in the Formation of a Porous Thorium–Organic Nanotube Suitable for Iodine Capture
Inorganic Chemistry ( IF 4.6 ) Pub Date : 2022-06-14 , DOI: 10.1021/acs.inorgchem.2c00427
Ashley M Hastings 1 , Debmalya Ray 2 , Sylvia L Hanna 3 , WooSeok Jeong 2 , Zhijie Chen 3 , Allen G Oliver 4 , Laura Gagliardi 5, 6 , Omar K Farha 3 , Amy E Hixon 1
Affiliation  

We report the synthesis, characterization, and iodine capture application of a novel thorium–organic nanotube, TSN-626, [Th6O4(OH)4(C6H4NO2)7(CHO2)5(H2O)3]·3H2O. The classification as a metal–organic nanotube (MONT) distinguishes it as a rare and reduced dimensionality subset of metal–organic frameworks (MOFs); the structure is additionally hallmarked by low node connectivity. TSN-626 is composed of hexameric thorium secondary building units and mixed O/N-donor isonicotinate ligands that demonstrate selective ditopicity, yielding both terminating and bridging moieties. Because hard Lewis acid tetravalent metals have a propensity to bind with electron donors of rival hardness (e.g., carboxylate groups), such Th–N coordination in a MOF is uncommon. However, the formation of key structural Th–N bonds in TSN-626 cap some of the square antiprismatic metal centers, a position usually occupied by terminal water ligands. TSN-626 was characterized by using complementary analytical and computational techniques: X-ray diffraction, vibrational spectroscopy, N2 physisorption isotherms, and density functional theory. TSN-626 satisfies design aspects for the chemisorption of iodine. The synergy between accessibility through pores, vacancies at the metal–oxo nodes, and pendent N-donor sites allowed a saturated iodine loading of 955 mg g–1 by vapor methods. The crystallization of TSN-626 diversifies actinide–MOF linker selection to include soft electron donors, and these Th–N linkages can be leveraged for the investigation of metal-to-ligand bonding and unconventional topological expressions.

中文翻译:

利用氮键形成适用于碘捕获的多孔钍-有机纳米管

我们报告了新型钍有机纳米管 TSN-626 [Th 6 O 4 (OH) 4 (C 6 H 4 NO 2 ) 7 (CHO 2 ) 5 (H 2 O )的合成、表征和碘捕获应用) 3 ]·3H 2O. 作为金属有机纳米管 (MONT) 的分类将其区分为金属有机框架 (MOF) 的稀有和降维子集;该结构还具有低节点连接性的特点。TSN-626 由六聚体钍二级结构单元和混合的 O/N 供体异烟酸酯配体组成,具有选择性双位性,同时产生终止和桥接部分。因为硬路易斯酸四价金属倾向于与硬度相媲美的电子供体(例如羧酸盐基团)结合,所以这种在 MOF 中的 Th-N 配位并不常见。然而,TSN-626 中关键结构 Th-N 键的形成覆盖了一些方形反棱柱金属中心,该位置通常被末端水配体占据。TSN-626 的特点是使用互补的分析和计算技术:2物理吸附等温线和密度泛函理论。TSN-626 满足碘化学吸附的设计要求。通过孔隙的可及性、金属-氧代节点处的空位和悬垂的 N 供体位点之间的协同作用使蒸汽法的饱和碘负载量达到 955 mg g -1。TSN-626 的结晶使锕系元素-MOF 连接体的选择多样化,包括软电子供体,这些 Th-N 连接可用于研究金属与配体的键合和非常规拓扑表达式。
更新日期:2022-06-14
down
wechat
bug