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Directing the Hetero-Growth of Lattice-Mismatched Surface Mounted Metal–Organic Frameworks by Functionalizing the Interface

Abstract

Heterostructured metal-organic framework materials (MOF-on-MOF or core-shell MOFs) feature synergistic properties of the hetero-architecture. Selective modification of the interface between the different MOF crystallites by mimicking a self assembled organic monolayer (SAM) of suitably functionalized isophatale (fu-ip) ligands allows for the oriented growth of the lattice-mismatched Cu2ndc2dabco@Cu3btc2 (A@B) using a stepwise liquid-phase epitaxial (LPE) deposition approach. Prior to growth of the hetero-structured surface mounted MOF (hetero-SURMOF), the binding configuration of a range of fu-ip ligands deposited at the external surface of SURMOF B was explored. Among many possibilities, only the configuration of fu-ip ligands in the “head-on” fashion binding on the external surface of SURMOF B proper exposition of the nucleation directing terminal functional groups is valid to act as template for the oriented hetero-growth of SURMOF A on top of SURMOF-B. The quartz crystal microbalance (QCM) frequency change profiles, the infrared reflection absorption spectra (IRRAS) and the water contact angle (WCA) measurements confirm the presence of the valid configuration of fu-ip on the external surface of SURMOF B. The fu-ip ligands containing the functional sidechain at the fifth position with long flexible aliphatic spacers and coordination active functional terminal groups reveals the most efficient for growing of porous, high-crystalline, lattice-mismatched hetero-SURMOFs. The concept is expected to be a good reference for the fabrication of other types of hetero-SURMOFs

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Publication details

The article was received on 26 Jun 2018, accepted on 04 Sep 2018 and first published on 04 Sep 2018


Article type: Paper
DOI: 10.1039/C8TA06136J
Citation: J. Mater. Chem. A, 2018, Accepted Manuscript
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    Directing the Hetero-Growth of Lattice-Mismatched Surface Mounted Metal–Organic Frameworks by Functionalizing the Interface

    R. A. Fischer, Z. Wang, S. Wannapaiboon, K. Rodewald, M. Tu and B. Rieger, J. Mater. Chem. A, 2018, Accepted Manuscript , DOI: 10.1039/C8TA06136J

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