A Robust Ultra-microporous Cationic Aluminiumbased Metal-Organic Framework with a Flexible Tetra-carboxylate Linker

Shyamapada Nandi (1, 2) , Asma Mansouri (1) , Iurii Dovgaliuk (1) , Philippe Boullay (3) , Gilles Patriarche (4) , Ieuan Cornu (5) , Pierre Florian (5) , Georges Mouchaham (1) , Christian Serre (1)

1 IMAP - Institut des Matériaux Poreux de Paris
2 VIT - Vellore Institute of Technology
3 CRISMAT - Laboratoire de cristallographie et sciences des matériaux
4 C2N - Centre de Nanosciences et de Nanotechnologies
5 CEMHTI - Conditions Extrêmes et Matériaux : Haute Température et Irradiation

Al-based cationic metal-organic frameworks (MOFs) are uncommon. Here, we report a cationic Al-MOF, MIP-213(Al) ([Al18(μ2-OH)24(OH2)12(mdip)6]6Cl•6H2O) constructed from flexible tetra-carboxylate ligand (5,5'-Methylenediisophthalic acid; H4mdip). Its crystal structure was determined by the combination of three-dimensional electron diffraction (3DED) and high-resolution powder X-ray diffraction. The structure is built from infinite corner-sharing chains of AlO4(OH)2 and AlO2(OH)3(H2O) octahedra forming an 18-membered rings honeycomb lattice, similar to that of MIL-96(Al), a scarce Al-polycarboxylate defective MOF. Despite sharing these structural similarities, MIP-213(Al), unlike MIL-96(Al), lacks the isolated μ3-oxo-bridged Al-clusters. This leads to an ordered defective cationic framework whose charge is balanced by Cl-sandwiched between two Al-trimers at the corner of the honeycomb, showing strong interaction with terminal H2O coordinated to the Al-trimers. The overall structure is endowed by a narrow quasi-1D channel of dimension ~4.7 Å. The Cl-in the framework restrains the accessibility of the channels, while the MOF selectively adsorbs CO2 over nitrogen and possesses high hydrolytic stability.

Mots clés: Metal-Organic Framework; Cationic MOF; Three-dimensional electron diffraction; Hydrolytically Stable; Environment-friendly Synthesis; CO2 Capture

Domaines: Matériaux

Shyamapada Nandi, Asma Mansouri, Iurii Dovgaliuk, Philippe Boullay, Gilles Patriarche, et al.. A Robust Ultra-microporous Cationic Aluminiumbased Metal-Organic Framework with a Flexible Tetra-carboxylate Linker. Communications Chemistry, 2023, 6 (1), pp.144. ⟨10.1038/s42004-023-00938-x⟩. ⟨hal-04303606⟩