Yadav Ankit K, Gładysiak Andrzej, Wolpert Emma H, Ganose Alex M, Samel-Garloff Bronson, Koley Dipankar, Jelfs Kim E, Stylianou Kyriakos C
Materials Discovery Laboratory (MaD Lab), Department of Chemistry, Oregon State University Corvallis OR 97331 USA
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London White City Campus, 82 Wood Lane W12 0BZ UK.
Chem Sci. 2024 Dec 11;16(6):2589-2599. doi: 10.1039/d4sc05037a. eCollection 2025 Feb 5.
The reaction between molybdenum(ii) acetate and 5-aminoisophthalic acid (HIso-NH) afforded [MoO(μ-O)(Iso-NH)], a novel molybdenum(v) metal-organic polyhedron (MOP) with a triangular antiprismatic shape stabilized by intramolecular N-H⋯O hydrogen bonds. The synthesis conditions, particularly the choice of solvent and reaction time, led to the precipitation of the Mo(v)-MOP in five distinct crystalline forms. These forms vary in their packing arrangements, co-crystallized solvent molecules, and counter-cations, with three phases containing dimethylammonium (dma) and the other two containing diethylammonium (dea). Each solvatomorph exhibits unique physical properties, including differences in porosity, and stability. These properties were discerned through empirical observations and supported by density functional theory calculations. Remarkably, the solubility of these MOP solvatomorphs in water was determined for the first time, with values of 4.30(2) g L for a (dma)[Mo(v)-MOP] phase, and 10.25(7) g L and 14.41(10) g L for two (dea)[Mo(v)-MOP] phases. Additionally, aqueous solutions of the Mo(v)-MOP were found to conduct electricity as weak electrolytes, showcasing their potential for applications in fields requiring partially ionized species.
醋酸钼（II）与5-氨基间苯二甲酸（HIso-NH）反应生成了[MoO(μ-O)(Iso-NH)]，这是一种新型的钼（V）金属有机多面体（MOP），呈三角反棱柱形状，通过分子内N-H⋯O氢键得以稳定。合成条件，特别是溶剂的选择和反应时间，导致了钼（V）-MOP以五种不同的晶体形式沉淀。这些形式在堆积排列、共结晶的溶剂分子和抗衡阳离子方面有所不同，其中三个相含有二甲基铵（dma），另外两个相含有二乙铵（dea）。每种溶剂化物都表现出独特的物理性质，包括孔隙率和稳定性的差异。这些性质通过经验观察得以辨别，并得到密度泛函理论计算的支持。值得注意的是，首次测定了这些MOP溶剂化物在水中的溶解度，对于一个（dma）[钼（V）-MOP]相，溶解度为4.30(2) g/L，对于两个（dea）[钼（V）-MOP]相，溶解度分别为10.25(7) g/L和14.41(10) g/L。此外，发现钼（V）-MOP的水溶液作为弱电解质能够导电，展示了它们在需要部分电离物种的领域中的应用潜力。
