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

“…So far, the formation and structure of SUM-81 have already demonstrated the capability of the bent TDHA ligand for differentiating coordination modes, compared to straight ligands. ,,, However, among all the possibilities shown in Scheme , only Mode II has been realized. Therefore, considering that increasing the radius of the metal node could further diversify the coordination environment, we explored more reactions with the same H 2 -TDHA ligand, but with In 3+ .…”

“…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).…”