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1.
Phys Chem Chem Phys ; 22(36): 20524-20530, 2020 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-32966417

RESUMO

Self-assembled ionic liquid crystals are anisotropic ionic conductors, with potential applications in areas as important as solar cells, battery electrolytes and catalysis. However, many of these applications are still limited by the lack of precise control over the variety of phases that can be formed (nematic, smectic, or semi/fully crystalline), determined by a complex pattern of different intermolecular interactions. Here we report the results of a systematic study of crystallization of several imidazolium salts in which the relative contribution of isotropic coulombic and directional H-bond interactions is carefully tuned. Our results demonstrate that the relative strength of directional H-bonds with respect to the isotropic Coulomb interaction determines the formation of a crystalline, semi-crystalline or glassy phase at low temperature. The possibility of pinpointing H-bonding directionality in ionic liquids make them model systems to study the crystallization of an ionic solid under a perturbed Coulomb potential.

2.
Inorg Chem ; 57(6): 3215-3222, 2018 Mar 19.
Artigo em Inglês | MEDLINE | ID: mdl-29509008

RESUMO

We have prepared two new lead halides with the novel general formula of DMA7Pb4X15 (DMA = [(CH3)2NH2]+ and X = Cl- or Br-) by using an easy route under mild conditions at room temperature. These compounds exhibit an unprecedented crystal structure, are formed by layers of distorted [PbX6] octahedra, which share corners and faces, and contain intercalated DMA cations. Very interestingly, they display dielectric transitions, which are related to a partial order-disorder process of the DMA cations between 160 and 260 K. Additionally, these new layered hybrids exhibit a broadband photoluminiscent emission, which is related to the structural distortions of the [PbX6] octahedra. These findings not only open up large possibilities for future optoelectronic applications of these materials, but they also offer a novel playground for an easy modulation of electrical and optical properties of hybrid organic-inorganic materials. We anticipate that this novel A7Pb4X15 formula can be adequate to tune the family of the hybrid lead halides using other alkylammonium cations, such as methylammonium, formamidinium, or ethylammonium, to improve their photoelectronic properties.

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