Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2 O Vapor Sorption

Ali Azmy; Shunran Li; Giasemi K Angeli; Claire Welton; Parth Raval; Min Li; Nourdine Zibouche; Lukasz Wojtas; G N Manjunatha Reddy; Peijun Guo; Pantelis N Trikalitis; Ioannis Spanopoulos

doi:10.1002/anie.202218429

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H₂ O Vapor Sorption

Angew Chem Int Ed Engl. 2023 Mar 13;62(12):e202218429. doi: 10.1002/anie.202218429. Epub 2023 Feb 10.

Authors

Ali Azmy¹, Shunran Li^{2

3}, Giasemi K Angeli⁴, Claire Welton⁵, Parth Raval⁵, Min Li⁶, Nourdine Zibouche⁷, Lukasz Wojtas¹, G N Manjunatha Reddy⁵, Peijun Guo^{2

3}, Pantelis N Trikalitis⁴, Ioannis Spanopoulos¹

Affiliations

¹ Department of Chemistry, University of South Florida, Tampa, FL 33620, USA.
² Department of Chemical and Environmental Engineering, Yale University, 9 Hillhouse Avenue, New Haven, CT 06520, USA.
³ Energy Sciences Institute, Yale University, 810 West Campus Drive, West Haven, CT 06516, USA.
⁴ Department of Chemistry, University of Crete, 71003, Heraklion, Greece.
⁵ University of Lille, CNRS, Centrale Lille Institut, Univ. Artois, UMR8181-UCCS-Unité de Catalyse et Chimie du Solide, 59000, Lille, France.
⁶ West Campus Materials Characterization Core, Yale University, New Haven, CT 06520, USA.
⁷ Department of Chemistry, University of Bath, Bath, BA2 7AY, UK.

PMID: 36656785
DOI: 10.1002/anie.202218429

Abstract

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with Pb^II in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)₂ Pb₅ Br₁₄ . The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H₂ O and D₂ O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H₂ O and D₂ O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors.

Keywords: Broad Light Emission; Gas Separation; Microporous Materials; Semiconductors; Water Stability.

Abstract

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