Al Isawi Wisam A, Philip Angel S, Singh Pooja, Zeller Matthias, Mezei Gellert
Department of Chemistry, Western Michigan University, Kalamazoo, Michigan 49008, United States.
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, United States.
Inorg Chem. 2025 Jan 20;64(2):1048-1063. doi: 10.1021/acs.inorgchem.4c04544. Epub 2025 Jan 3.
The supramolecular binding exclusively by H-bonds of SeO, MoO and WO ions to form nanojars of the formula [EO⊂{-Cu(μ-OH)(μ-pz)}] (; E = Se, Mo, W; = 28-34; pz = pyrazolate) was studied in solution by electrospray ionization mass spectrometry, variable temperature, paramagnetic H NMR and UV-vis spectroscopy, and in the solid state by single-crystal X-ray crystallography. These large anions allow for the observation of a record nanojar size, (E = Mo, W). Six crystal structures are described of nanojars of varying sizes with either SeO, MoO or WO entrapped ions, including the first example of a cocrystal of two different nanojars in crystallographically unique positions, and . The latter provides unprecedented structural information about the Cu+Cu+Cu ring combination of a nanojar with an entrapped tetrahedral anion. Also, the first crystal structure of a supramolecular host-guest complex with an entrapped WO ion, is reported in this work. The relative strength of binding of SeO, MoO and WO ions by nanojars of different sizes was assessed by reactivity studies toward Ba ions and NH. Thermal stability studies of the various nanojars were conducted in DMSO- solutions over a 22-150 °C range. Furthermore, liquid-liquid extraction of SeO, MoO and WO ions from water into an organic solvent by nanojars was investigated.
通过电喷雾电离质谱、变温、顺磁氢核磁共振和紫外可见光谱等方法在溶液中研究了SeO、MoO和WO离子仅通过氢键形成分子式为[EO⊂{-Cu(μ-OH)(μ-pz)}]（E = Se、Mo、W； = 28 - 34；pz = 吡唑酸酯）的纳米罐的超分子结合情况，并通过单晶X射线晶体学在固态下进行了研究。这些大阴离子使得能够观察到创纪录的纳米罐尺寸（E = Mo、W）。描述了六种包含被困SeO、MoO或WO离子的不同尺寸纳米罐的晶体结构，包括两个处于晶体学独特位置的不同纳米罐的共晶体的首个实例，即 和 。后者提供了关于带有被困四面体阴离子的纳米罐的Cu⁺Cu⁺Cu环组合的前所未有的结构信息。此外，本工作还报道了带有被困WO离子的超分子主客体复合物的首个晶体结构 。通过对Ba离子和NH的反应性研究评估了不同尺寸纳米罐对SeO、MoO和WO离子的相对结合强度。在22 - 150°C范围内，在二甲基亚砜溶液中对各种纳米罐进行了热稳定性研究。此外，还研究了纳米罐将SeO、MoO和WO离子从水液 - 液萃取到有机溶剂中的情况。
