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Multistep Structural Transformation of a Magnetic Metal–Organic Framework: Possible Transformation Mechanism, Form Evolution, and Magnetic Properties

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journal contribution
posted on 09.01.2020, 20:33 by Dong-Li Meng, Xue Wang, Chong-Bin Tian, Wei Wei, Shao-Wu Du
A new cluster-based heterometallic metal–organic framework, [Mn3Li2(TBIP)4­(DMF)4] (1) (H2TBIP = 5-tert-butylisophthalic acid), was solvothermally synthesized. Triggered by methanol, the α-Po network of 1 underwent a sequence of irreversible structural transformation to form a CdSO4-type framework [Mn­(TBIP)­(H2O)3]­·4H2O­(5), during which course three intermediate phases, 24 were observed. A single crystal X-ray diffraction analysis reveals that 4, formulated as [Mn3(TBIP)3­(MeOH)4], exhibits the same topology network of 1 but with a different node structure. Notably, the evolution of form from microcrystals 1 to diverse forms, including core–shell and Janus-type heterostructures, was achieved by controlling the time of methanol immersion. Moreover, the overall structural transformation from 1 to 5 was monitored by magnetic susceptibility, scanning electron microscopy, inductively Coupled Plasma analysis, and electron paramagnetic resonance, which provide useful information for understanding the mechanism of this transformation.