A siderophore-inspired two-dimensional Fe–hydroxamate metal–organic framework

Abstract

Inspired by hydroxamate-based siderophores, here we report the synthesis of a novel two-dimensional (2D) Fe-hydroxamate metal-organic framework (MOF), namely SUM-31. The MOF, constructed from homoleptic Fe(hydroxamate)3 nodes and linear E-ethylenedihydroxamate...

Structural Diversity in Ga/In-Hydroxamate Metal–Organic Materials

“…These structural characteristics at the metal vertices and the bridging ligands caused the MOP to deviate from a perfect cube. Like previous findings in Fe-hydroxamate MOMs, , the homoleptic Ga(hydroxamate) 3 nodes also conform to a C 3 symmetry. In the overall meso compound, there are equal amounts of Δ and Λ configurations (four for each) that are distributed in an alternating fashion on the SUM-81 cuboid (Figure S8).…”

“…As one of the emerging subcategories with outstanding chemical robustness, MOMs based on chelating hydroxamate groups have begun to garner research attention. − In comparison to carboxylic acid ligands which are the most common MOM building blocks (based on statistical analysis of the Cambridge Structural Database), hydroxamic acid ligands have stronger metal–ligand interactions due to their chelating nature. All reported MOMs based on hydroxamates so far have demonstrated excellent chemical stability, including compatibility with various organic solvents and aqueous solutions.…”

Engineered Nanoporous Frameworks for Adsorption Cooling Applications

“…As proposed by Xie et al, 271 the adsorption performance of guest molecules over two-dimensional conductive MOFs could be enhanced via "through-bond", "extended conjugation", and "through-space" approaches using charge transport pathways in continuous chains of coordination bonds between the metal centers and the ligands' functional groups, large delocalized systems between the metals and the entire ligands, and π−π stacking interactions between the organic moieties, respectively. Meanwhile, novel two-dimensional conductive MOFs, including SUM-1 (node, Zr 4+ ; linker, benzene-1,4-dihydroxamate), 272 SUM-6/7 (node, Ce 3+ ; linker, benzene-1,4-dihydroxamate), 273 SUM-9 (node, In 3+ ; linker, benzene-1,4-dihydroxamate), 274 and SUM-31 (node, Fe 3+ ; linker, E-ethylenedihydroxamate), 275 have shown excellent stability and high performance for gas adsorption, gas separation, and electrochemical sensing. Thus, nanoporous sorbents with low dimensions and increased conductivity, specifically thermal conductivity, may be an excellent option for boosting the adsorption cooling performance.…”

Sacrificial-Hydroxamate-Enabled Sizable Crystallization of Scandium Carboxylate Metal–Organic Frameworks

“…As observed in many biological and chemical scenarios, hydroxamates have demonstrated strong chelating capabilities toward metals. In fact, this knowledge has also been reflected in recent MOF examples featuring hydroxamate-chelated M III /M IV building blocks, with outstanding chemical robustness. − At the same time, hydroxamates are prone to hydrolytic transformation into corresponding carboxylates, , suggesting that it is a suitable candidate as a sacrificial modulating ligand, as shown in Scheme .…”

“…Our first target was the benchmark MOF MIL-88 . As shown in Figure a, pairing Sc­(OTf) 3 (OTf = trifluoromethanesulfonate) with ( E )-ethylene-1,2-dihydroxamic acid (H 2 -EDHA for MIL-88A) or benzene-1,4-dihydroxamic acid (H 2 -BDHA for MIL-88B), along with HNO 3 , which is known to promote the hydrolysis of hydroxamates, , we were able to prepare MIL-88A/B (Sections 2.1–2.4) in pure phases (Figure b,c). Comparing to samples prepared from reported conventional synthetic protocols, , significant enlargement of the MIL-88A/B crystals was observed (Figures S3–S6).…”