A flexible interpenetrating coordination framework with a bimodal porous functionality

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Introducing a functional part into open-framework materials that tunes the pore size/shape and overall porous activity will open new routes in framework engineering and in the fabrication of new materials. We have designed and synthesized a bimodal microporous twofold interpenetrating network {[Ni(bpe)2(N(CN)2)](N(CN)2)(5H2O)}n (1), with two types of channel for anionic N(CN)2 (dicyanamide) and neutral water molecules, respectively. The dehydrated framework provides a dual function of specific anion exchange of free N(CN)2 for the smaller N3 anions and selective gas sorption. The N3-exchanged framework leads to a dislocation of the mutual positions of the two interpenetrating frameworks, resulting in an increase in the effective pore size in one of the counterparts of the channels and a higher accommodation of adsorbate than in the as-synthesized framework (1), showing the first case of controlled sorption properties in flexible porous frameworks.

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Figure 1: X-ray crystal structure of {[Ni(bpe)2(N(CN)2)](N(CN)2)(5H2O)}n (1).
Figure 2: XRPD patterns in different states.
Figure 3: Morphology of the crystal of {[Ni(bpe)2(N(CN)2)](N(CN)2)(5H2O)}n in different states.
Figure 4: Adsorption isotherm for vapour adsorption in {[Ni(bpe)2(N(CN)2)](N(CN)2)}n (1a).
Figure 5: Adsorption isotherm for vapour adsorption in {[Ni(bpe)2(N(CN)2)](N(CN)2)}n (1a).
Figure 6: Nanospace engineering by anion exchange.


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This work was supported by Grants-in-Aid for Scientific Research in a Priority Area ‘Chemistry of coordination space’ (434) and a CREST/JST programme from the Ministry of Education, Culture, Sports, Science and Technology, Government of Japan.

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Correspondence to Susumu Kitagawa.

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Supplementary Information, Fig S1

Supplementary Information; Figures S1-S8; Tables S1, S2 (PDF 1055 kb)

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