Inside polyMOFs: layered structures in polymer-based metal-organic frameworks

In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2020-10, Vol.11 (38), p.1523-1528
Main Authors: Bentz, Kyle C, Gnanasekaran, Karthikeyan, Bailey, Jake B, Ayala, Sergio, Tezcan, F. Akif, Gianneschi, Nathan C, Cohen, Seth M
Format: Article
Language:English
Subjects:
Chemistry
Copolymers
Crystal structure
Crystallinity
Electron microscopy
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Lamellar structure
Mass ratios
MATERIALS SCIENCE
Metal-organic frameworks
Microscopy
Polyethylene glycol
Polymers
Self-assembly
Small angle X ray scattering
Synchrotron radiation
Synchrotrons
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Summary:In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism. A variety of techniques were employed to interrogate the internal structure of the polyMOFs, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and small-angle synchrotron X-ray scattering (SAXS). Independent of the copolymer architecture or composition, the internal structure of the polyMOF crystals showed similar lamellar self-assembly at single-nanometer length scales. In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks.
ISSN:2041-6520
2041-6539
DOI:10.1039/d0sc03651j