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Issue 34, 2015
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Porous frameworks constructed by non-covalent linking of substitution-inert metal complexes

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Abstract

The incorporation of active sites into metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) is an attractive way to functionalise these materials. However, the methodology to organise substitution-inert metal-based secondary building units (SBUs) with active sites into MOFs or PCPs via coordination driven self-assembly is severely limited. In this study, we successfully assembled substitution-inert paddle-wheel Rh(II) dimers to afford three novel porous frameworks, Rh2(ppeb)4(THF)2 (1-THF), Rh2(ppeb)4(3-pentanone)2 (1-PN) and Rh2(ppeb)4(1-adamantylamine)2 (1-AD) (ppeb = 4-[(perfluorophenyl)ethynyl]benzoate), by using non-covalent interactions. Multipoint arene–perfluoroarene (Ar–ArF) interactions, which allow the unidirectional face-to-face interaction mode of aromatic rings, were used to assemble the substitution-inert paddle-wheel Rh(II) dimers. The obtained frameworks were structurally characterisation by single crystal X-ray diffraction, and it is found that all structures exhibited a one-dimensional channel with active axial sites exposed to the pores. The porous properties of the obtained frameworks were also investigated by thermogravimetric analysis, gas adsorption and powder X-ray diffraction measurements. Moreover, the ligand substitution reaction at the active axial sites was examined at the crystalline state and the flexible structural transformation with the change of channel shapes and sizes was observed.

Graphical abstract: Porous frameworks constructed by non-covalent linking of substitution-inert metal complexes

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Supplementary files

Article information


Submitted
30 Apr 2015
Accepted
17 Jul 2015
First published
21 Jul 2015

This article is Open Access

Dalton Trans., 2015,44, 15334-15342
Article type
Paper
Author version available

Porous frameworks constructed by non-covalent linking of substitution-inert metal complexes

T. Itoh, M. Kondo, H. Sakamoto, K. Wakabayashi, M. Kanaike, K. Itami and S. Masaoka, Dalton Trans., 2015, 44, 15334
DOI: 10.1039/C5DT01620G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
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    [Original citation] - Published by the PCCP Owner Societies.
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    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

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