Journal of the American Chemical Society · 2008 · 490 citations · 15 references
Natural SciencesChemistryMaterials ScienceCondensed Matter PhysicsInorganic ChemistrySolid State PhysicsCrystal ChemistryCrystallographyFerroelectric MaterialsPerovskite MaterialsPhase TransitionsX-ray CrystallographyDielectric ConstantOrder-disorder Phase DiagramOrder-disorder Phase TransitionOrganic-inorganic Hybrid PerovskitesPerovskite Crystal StructurePowder DiffractionPowder Diffraction AnalysisPowder X-ray Diffraction
[(CH3)2NH2]Zn(HCOO)3, 1, adopts a structure that is analogous to that of a traditional perovskite, ABX3, with A = [(CH3)2NH2], B = Zn, and X = HCOO. The hydrogen atoms of the dimethyl ammonium cation, which hydrogen bond to oxygen atoms of the formate framework, are disordered at room temperature. X-ray powder diffraction, dielectric constant, and specific heat data show that 1 undergoes an order-disorder phase transition on cooling below 156 K. We present evidence that this is a classical paraelectric to antiferroelectric phase transition that is driven by ordering of the hydrogen atoms. This sort of electrical ordering associated with order-disorder phase transition is unprecedented in hybrid frameworks and opens up an exciting new direction in rational synthetic strategies to create extended hybrid networks for applications in ferroic-related fields.
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