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Post‐synthetic modification unlocks a 2D‐to‐3D switch in MOF breathing response: a single‐crystal‐diffraction mapping study

DOI: 10.1002/anie.202105272 DOI Help

Authors: Lee Brammer (University of Sheffield) , Elliot J. Carrington (The University of Sheffield) , Stephen F. Dodsworth (The University of Sheffield) , Sandra Van Meurs (The University of Sheffield) , Mark R. Warren (Diamond Light Source)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Angewandte Chemie International Edition

State: Published (Approved)
Published: June 2021

Abstract: Post-synthetic modification (PSM) of the interpenetrated diamondoid metal-organic framework (Me 2 NH 2 )[In(BDC-NH 2 ) 2 ] (BDC-NH 2 = aminobenzenedicarboxylate) SHF-61 proceeds quantitatively in a single-crystal-to-single-crystal manner to yield the acetamide derivative (Me 2 NH 2 )[In(BDC-NHC(O)Me) 2 ] SHF-62 . Continuous breathing behaviour during activation/desolvation is retained upon PSM, but pore closing now leads to ring-flipping to avert steric clash of amide methyl groups of the modified ligands. This triggers a reduction in the amplitude of the breathing deformation in the two dimensions associated with pore diameter, but a large increase in the third dimension associated with pore length. The MOF is thereby converted from predominantly 2D breathing (in SHF-61 ) to a distinctly 3D breathing motion (in SHF-62 ) indicating a decoupling of the pore-width and pore-length breathing motions. These breathing motions have been mapped by a series of single-crystal diffraction studies.

Journal Keywords: metal-organic framework; Single-Crystal; Breathing; Anisotropic; Post-Synthetic Modification

Subject Areas: Chemistry, Materials

Instruments: I11-High Resolution Powder Diffraction , I19-Small Molecule Single Crystal Diffraction

Discipline Tags:

Material Sciences Metallurgy Metal-Organic Frameworks Chemistry Organometallic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD) X-ray Powder Diffraction