Layered organic-inorganic perovskites form a class of materials composed of an anionic 2D perovskite slab templated by a layer of organic ammonium cations which form hydrogen bonds with the halides in the inorganic sublattice. By using bifunctional organic ammonium cations, we report a synthetic strategy for templating the recurrent intergrowth of non-isostructural inorganic sublattices in layered perovskite single crystals. By single-crystal X-ray diffraction, we find that alkylammonium zwitterions, an asymmetric ammonium dication, and a coordinating alkylammonium cation can all be used to direct the growth of layered perovskite heterostructures. The zwitterionic taurine (2-(ammonioethyl)sulfonate) templates three unique perovskite intergrowths based on H3O+, Li+, and Mg2+. Notably, the extended sulfonate sublattices of lithium and magnesium are strikingly similar to Li2SO4 and MgSO4. The histammonium dication templates the intergrowth of an unusual [CuCl2]n– chain between [CuInCl8]4– slabs. Finally, we report two layered lead halide perovskite intergrowths that include a lead halide slab similar to the PbX2 structure type. By comparing the intergrown sublattices to isostructural sublattices in non-intergrowth crystals, we envison the a stepwise deconstruction of the observed materials from known dimensionally reduced phases which inturn related to inorganic partent structures of higher connectivity. We find the particularly large cell constants of perovskite slabs allow for the intergrowth of relatively complex structures, and large in-plane lattice strains can be accommodated in comparison to typical lattice mismatch parameters calculated for oxide intergrowths. From this, the discovery of other structure types capable of forming atom perfect heterointerfaces with the halide perovskites may be directed by by analogy to these exemplary structures. More broadly, the templated formation of non-isostructural halide perovskite intergrowths may greatly expand the diversity of chemical and electronic structures possible within this class of technologically important materials.

Crystallization of layered perovskite heterostructures using bifunctional organic templates

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.