Crystalline bilayers unzipped and rezipped: solid-state reaction cycle of a metal–organic framework with triple rearrangement of intralayer bonds
| Autor: | Maria Bałanda, Kornel Roztocki, Dariusz Matoga, Franziska Emmerling, Marcin Oszajca, Magdalena Fitta, Manuel Wilke |
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| Rok vydání: | 2017 |
| Předmět: |
Diffraction
chemistry.chemical_element 02 engineering and technology Manganese 010402 general chemistry Isonicotinic acid 01 natural sciences law.invention Reaction rate chemistry.chemical_compound symbols.namesake law Mechanochemistry General Materials Science chemistry.chemical_classification General Chemistry Polymer 021001 nanoscience & nanotechnology Condensed Matter Physics Synchrotron 0104 chemical sciences Crystallography chemistry symbols 0210 nano-technology Raman spectroscopy |
| Zdroj: | CrystEngComm. 19:2987-2995 |
| ISSN: | 1466-8033 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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