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Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds

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Abstract

We present a series of remarkable structural transformations for a family of layered metal–organic frameworks (MOFs) in a three-step solid-state reaction cycle. The cycle represents new dynamic behavior of 2D coordination polymers and involves the sequence of reactions: {[Mn2(ina)4(H2O)2]·2EtOH}n (JUK-1) → {(NH4)2[Mn(ina)2(NCS)2]}n·xH2O (JUK-2) → {[Mn2(ina)2(Hina)2(NCS)2]}n (JUK-3) → JUK-1 (Hina = isonicotinic acid), each accompanied by rearrangement of intralayer coordination bonds and each induced by a different external stimulus. In situ investigation of the first step of the cycle by combined synchrotron X-ray diffraction and Raman spectroscopy reveals direct mechanochemical unzipping of JUK-1 bilayers to respective JUK-2 layers with reaction rates dependent on the milling conditions. In contrast, the reverse zipping of JUK-2 layers involves two steps and proceeds through a new MOF (JUK-3) whose structure was elucidated by powder X-ray diffraction. Magnetic measurements confirm conversions of manganese nodes in the reaction cycle. The findings indicate the possibility of developing coordination-based assemblies with large structural responses for use in smart stimuli-responsive systems and sensor technologies.

Graphical abstract: Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds

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Publication details

The article was received on 05 Apr 2017, accepted on 03 May 2017 and first published on 03 May 2017


Article type: Paper
DOI: 10.1039/C7CE00655A
Citation: CrystEngComm, 2017, Advance Article
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    Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds

    D. Matoga, K. Roztocki, M. Wilke, F. Emmerling, M. Oszajca, M. Fitta and M. Bałanda, CrystEngComm, 2017, Advance Article , DOI: 10.1039/C7CE00655A

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