Controlling phase transition of low-dimensional perovskites through halogen-halogen interactions

Anastasios Stergiou^a, Gabriella Cavallo^a, Pierangelo Metrangolo^a

^aSupraBioNanoLab, Department of Chemistry, Materials, and Chemical Engineering “Giulio Natta”, Politecnico di Milano, via L. Mancinelli 7, 20131 Milan, Italy

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS Fall 2024 Conference (MATSUSFall24)

#PeroMAT- Halide perovskite and perovskite- inspired materials: synthesis and applications

Lausanne, Switzerland, 2024 November 12th - 15th

Organizers: Raquel Galian, Lakshminarayana Polavarapu and Paola Vivo

Oral, Anastasios Stergiou, presentation 246
DOI: https://doi.org/10.29363/nanoge.matsusfall.2024.246
Publication date: 28th August 2024

In two-dimensional hybrid organic-inorganic metal halide perovskites (2D-HOIPs), the stacking setting of the adjacent inorganic sheets is influenced by the nature of the incorporated organic cation. [1-2] The photophysical properties of 2D-HOIPs can be accordingly tuned. However, the structural properties of 2D-HOIPs are more complex than the parent 2D metal oxide perovskites because of the larger size of the organic cations, their different chemical and structural properties. For instance, an order-disorder transition of the cation may result to a ferroelectric phase, [3] while octahedral distortion can modulate photophysical and electrical properties of the HOIP. [4] In this context, octahedral distortion as well as cation’s distortion urges for a systematic understanding of the crystallographic properties of 2D-HOIPs. [5]

In recent years, implementation of iodine-terminated alkylammonium cations is attracting a lot of interest, since it has been proposed that the development of halogen-halogen supramolecular interactions between the iodine atom of the organic cation (acting as halogen bond, XB, donor) and the apical inorganic iodine atoms of the inorganic sheets (acting as halogen bond, XB, acceptors) suppress phase transitions towards undesired lower-symmetry phases. [6] The rich halogen chemistry of metal halide perovskite semiconductors brings such halogen bond (XB) strategies under the spotlight, [7] while halogen-halogen interactions, in general, may lead also to unprecedented properties. [8] Herein, a bimodal iodine-terminated alkylammonium cation has been studied as a supramolecular modulator of the crystalline organization of a 2D-HOIP. Utilizing heat as an external stimulus a controlled and reversible single crystal-to-single-crystal phase transition was observed. Controlling the conformation of the cation, the modulation of the interlayer XB formation was achieved. The new perovskite phase has discrete structural and photophysical properties, as evidenced by variable temperature investigation by single-crystal X-ray diffraction, solid-state NMR, UV-Vis and photoluminescence spectroscopies.

References:

[1] Stoumpos, C.; Cao, D.; Clark, D.; Young, J.; Rondinelli, J.; Jang, J.; Hupp, J.; Kanatzidis, M. Ruddlesden−Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors. Chem. Mater. 2016, 28, 2852−2867

[2] Mao, L.; Weijun Ke, W.; Pedesseau, L.; Wu, Y.; Katan, C.; Even, J.; Wasielewski, M.; Stoumpos, C.; Kanatzidis, M. Hybrid Dion−Jacobson 2D Lead Iodide Perovskites. J. Am. Chem. Soc. 2018, 140, 3775−3783

[3] Weller, M.; Weber, O.; Henry, P.; Di Pumpoac, A.; Hansen, T. Complete structure and cation orientation in the perovskite photovoltaic methylammonium lead iodide between 100 and 352 K. Chem. Commun. 2015, 51, 4180-4183

[4] McNulty, J.; Lightfoot, P. Structural chemistry of layered lead halide perovskites containing single octahedral layers. IUCrJ 2021, 8, 485-513

[5] Park, I.-H.; Qiannan Zhang, Q.; Chang Kwon, K.; Zhu, Z.; Wei, Z.; Kai Leng, Y.; Giovanni, D.; Seob Choi, H.; Ibrahim Abdelwahab, I.; Xu, Q.-H.; Chien Sum, T.; Loh, K. Ferroelectricity and Rashba Effect in a Two-Dimensional Dion-Jacobson Hybrid Organic–Inorganic Perovskite. J. Am. Chem. Soc. 2019, 141 (40), 15972–15976

[6] Chakraborty, R.; Sheikh, T.; Nag, A. Iodine−Iodine Interactions Suppressing Phase Transitions of 2D Layered Hybrid (I-(CH2)n‑NH3)2PbI4 (n = 2−6) Perovskites. Chem. Mater. 2022, 34, 288−296

[7] Metrangolo, P.; Canil, L.; Abate, A.; Terraneo, G.; Cavallo, G. Halogen Bonding in Perovskite Solar Cells: A New Tool for Improving Solar Energy Conversion. Angew. Chem. Int. Ed. 2022, 61(11), e202114793

[8] Stergiou, A.; Leccioli, L.; Ricci, D.; Zaffalon, M.; Brovelli, S.; Baldelli Bombelli, F.; Terraneo, G.; Cavallo, G.; Metrangolo, P. Perovskite-like Liquid-Crystalline Materials Based on Polyfluorinated Imidazolium Cations. Angew. Chem. Int. Ed. 2024, e202408570 (Accepted Article)

Acknowledgements:

We acknowledge the financial support from the European Union’s Horizon Europe research and innovation program, under the MSCA grant agreement No 101059015, acronym HaloCell.

The powder and small/wide angle X-ray diffraction experiments were carried out at the NeXt-GAME Laboratory of the Politecnico di Milano, co-funded by Regione Lombardia.

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