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Order-Disorder Phase Transitions and Topological Isomerization in a Ternary-Ligand Synergistic Coordination Network
Chen Shang1, Ting Xu1, Tong Liu1
1TKL of Organic Solar Cells and Photochemical Conversion, School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, P. R. China.
Abstract:
Recently, supramolecular isomers obtained by single-crystal-to-single-crystal (SCSC) transformations have emerged as a significant research focus but are rarely reported. To address this, a lon topological complex, [H2DABCO][FeII2(C2O4)(HCOO)2Cl2]·H2O (1), was synthesized with a cation dynamics nature, in which the [H2DABCO]2+ underwent an order-disorder transition on heating at about 210 K, accompanied by significant dielectric anomalies. Upon further heating above 413 K, 1 undergoes an intriguing SCSC transformation to the anhydrous phase [H2DABCO][FeII2(C2O4)(HCOO)2Cl2] (2), retaining the original coordination geometry of the metal ions and ligands but revealing the zeolite crb net. This supramolecular network isomerization is extremely rare during the single-crystal-to-single-crystal transformation. Besides, the isomerization of the topological network influences the structural phase transitions and magnetic properties of 1 and 2. In 2, the organic ammonium ions remain disordered below 100 K without further structural phase transitions. Magnetic studies further reveal that 1 is an antiferromagnet with an ordering temperature of 25 K and exhibits canting at 15 K, while in 2, no significant spin canting was observed.
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