Role of a-site molecular ions in the polar functionality of metal–organic framework perovskites

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dc.contributor.authorLu, Ten_AU
dc.contributor.authorCortie, DLen_AU
dc.contributor.authorLi, ZXen_AU
dc.contributor.authorNarayanan, Nen_AU
dc.contributor.authorLiu, Zen_AU
dc.contributor.authorSun, QBen_AU
dc.contributor.authorFrankcombe, TJen_AU
dc.contributor.authorMcIntyre, GJen_AU
dc.contributor.authorYu, Den_AU
dc.contributor.authorLiu, Yen_AU
dc.date.accessioned2024-05-15T06:36:47Zen_AU
dc.date.available2024-05-15T06:36:47Zen_AU
dc.date.issued2021-12-28en_AU
dc.date.statistics2024-05-15en_AU
dc.description.abstractRecent studies on organic–inorganic hybrid perovskites (OIHPs) and ferroelectric metal–organic framework perovskites (MOFPs) reveal their superb performance as highly efficient materials for photovoltaics and ferroelectrics. This has enabled the development of a new generation of optic-electronic-mechanical devices based on green chemistry. However, the fundamental understanding of these polarization-related functionalities is not yet clear, which has hindered the progress in further designing and developing materials with expected properties. In this work, we investigate three MOFPs that have the same Mg(HCOO)3– frameworks with different molecular ions: [CH3NH3][Mg(HCOO)3] (MA-MOF), [(CH3)2NH2][Mg(HCOO)3] (DMA-MOF), and [C(NH2)3][Mg(HCOO)3] (GUA-MOF). Single-crystal and powder X-ray diffraction, inelastic neutron spectroscopy, and ab initio molecular dynamics simulations are combined to achieve a detailed description of the three MOFPs’ static and dynamic structures as a function of temperature. Intriguingly, our study reveals that the alignments and motions of the guest molecular ions are highly dependent on the directional hydrogen bonds that link N–H units to the surrounding MgO6 octahedra through the O acceptor from the frameworks. At the same time, the size, dynamic behavior, and alignments of the A-site molecular ions influence the distortive framework structures and their temperature-dependent deformation. Therefore, the mutual interaction between the guest and the framework determines the overall functionalities of the MOFPs. This study indicates that the configuration of the A-site molecular ions and the potential hydrogen bonds are critical to design the polar functionalities in both MOFPs and OIHPs. © 2021 American Chemical Societyen_AU
dc.identifier.citationLu, T., Cortie, D., Li, Z.-X., Narayanan, N., Liu, Z., Sun, Q., Frankcombe, T. J., McIntyre, G. J., Yu, D., & Liu, Y. (2021). Role of a-site molecular ions in the polar functionality of metal–organic framework perovskites. Chemistry of Materials, Vol. 33(24), pp. 9666-9676. DOI: 10.1021/acs.chemmater.1c03276en_AU
dc.identifier.issn0897-4756en_AU
dc.identifier.issn1520-5002en_AU
dc.identifier.issue24en_AU
dc.identifier.journaltitleChemistry of Materialsen_AU
dc.identifier.pagination9666-9676en_AU
dc.identifier.urihttps://doi.org/10.1021/acs.chemmater.1c03276en_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/15605en_AU
dc.identifier.volume33en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherAmerican Chemical Society (ACS)en_AU
dc.relation.urihttps://doi.org/10.1021/acs.chemmater.1c03276en_AU
dc.subjectPerovskitesen_AU
dc.subjectFerroelectric materialsen_AU
dc.subjectPolarizationen_AU
dc.subjectX-ray diffractionen_AU
dc.subjectNeutron spectroscopyen_AU
dc.subjectMolecular ionsen_AU
dc.subjectHydrogenen_AU
dc.titleRole of a-site molecular ions in the polar functionality of metal–organic framework perovskitesen_AU
dc.typeJournal Articleen_AU
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