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| Home > Publications database > Indium Imidazolate Frameworks with Differently Distorted $ReO_{3}$-Type Structures: Syntheses, Structures, Phase Transitions, and Crystallization Studies |
| Home > Publications database > Indium Imidazolate Frameworks with Differently Distorted $ReO_{3}$-Type Structures: Syntheses, Structures, Phase Transitions, and Crystallization Studies |
| Journal Article | PUBDB-2014-04189 |
; ; ; ; ;
2014
ACS Publ.
Washington, DC
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Please use a persistent id in citations: doi:10.1021/cg5007499
Abstract: Three indium imidazolates have been preparedby employing solvothermal, ionothermal, and solventlesssyntheses. The crystal structures have been determined usinglaboratory powder XRD methods in combination with DFTcalculations. In phases I−III, octahedrally coordinated In(III)ions are bridged by imidazolate (im) ligands into 3Dframeworks that are related to distorted filled-ReO3 (ABX3perovskite) structures with different octahedron tilting.Clathrate-type phases I (cubic space group Im3̅) and II(trigonal R3̅) may be formulated as [A′A″3In4(im)12] andcontain two types of cubic cages, A′ and A″, which may hostguest molecules and are occupied by im moieties, respectively. A reversible structural phase transition between low-temperaturephase II and high-temperature phase I, occurring on heating at about 90 °C, was studied by DSC and variable-temperaturepowder XRD experiments. Depending on the synthesis, more specifically on the nature and amount of guests trapped in the A′cages, the phase transition was suppressible, enabling I to be recovered at room temperature. Phase III (trigonal R3̅) may beformulated as [AIn(im)3]. It is a dense phase in which the cubic A cages are occupied by im moieties. For the first time, theionothermal formation of a coordination polymer, phase III, was monitored in situ by time-resolved EDXRD experiments. Rateconstants and activation energies for both nucleation and crystal growth, as estimated by kinetic analysis of the EDXRD data, arecompared to corresponding values reported previously for the solvothermal crystallization of other coordination polymers.
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