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Research Article

Solid-state phase transformations toward a metal-organic framework of 7-connected Zn4O secondary building units

Jaehui Kim, Junsu Ha, Jae Hwa Lee( ), Hoi Ri Moon( )
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
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Abstract

In the development of metal-organic frameworks (MOFs), secondary building units (SBUs) have been utilized as molecular modules for the construction of nanoporous materials with robust structures. Under solvothermal synthetic conditions, dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures. Alternatively, MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state. In this sense, we studied the solid-state transformation of two ndc-based Zn-MOFs (ndc = 1,4-naphthalene dicarboxylate) with different SBUs but the same pcu topology to another MOF with sev topology. One of the chosen MOFs with pcu nets is [Zn2(ndc)2(bpy)]n (bpy = 4,4’-bipyridine), (6Cbpy-MOF) consisting of a 6-connected pillared-paddlewheel SBU, and the other is IRMOF-7 composed of 6-connected Zn4O(COO)6 SBUs and ndc. Upon post-structural modification, these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zn4O(COO)7 SBU (7C-MOF). The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined. In addition, the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity, which determines the inertness during the solid-state phase transformation. This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.

Keywords

metal-organic frameworksecondary building unitssolid-state transformationlinker basicityligand addition reaction

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Nano Research
Volume 14 Issue 2,
February 2021
Pages 411-416
DOI: 10.1007/s12274-020-2873-y
Cite this article:
Kim J, Ha J, Lee JH, et al. Solid-state phase transformations toward a metal-organic framework of 7-connected Zn4O secondary building units. Nano Research, 2021, 14(2): 411-416. https://doi.org/10.1007/s12274-020-2873-y
Topics:
MetalsOrganic frameworks Organic polymersOrganometallicsPorous materialsTopology

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Received: 04 March 2020
Revised: 22 April 2020
Accepted: 11 May 2020
Published: 09 June 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
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