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Intralayer bidentate diammoniums for stable two-dimensional perovskites

Nature Chemistry volume 18, pages 275–282 (2026)Cite this article

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Abstract

Two-dimensional (2D) metal halide perovskites have attracted considerable attention for optoelectronic applications. Conventional 2D perovskites include Ruddlesden–Popper (R-P), Dion–Jacobson (D-J) and alternating cation phases. Here we introduce a class of 2D perovskite incorporating intralayer bidentate ligands, termed B-D phase perovskites, designed to enhance structural diversity and stability. We synthesized bidentate ligands with a rigid core unit and two ipsilateral ammonium-terminated linker groups, and obtained single crystals incorporating these B-D ligands with intralayer bidentate coordination. Molecular dynamics simulations reveal that the B-D ligand exhibits stronger binding energies to the inorganic layer compared with its R-P and D-J phase counterparts. Polycrystalline thin films of B-D phase showed superior thermal resistance, outperforming R-P and D-J phase analogues by 1,600% and 140% respectively, based on absorption stability assessments. Photovoltaic devices incorporating the B-D ligand exhibited higher power conversion efficiency and extended stability. These findings establish B-D phase 2D perovskites as a promising platform for next-generation optoelectronic applications, advancing ligand engineering for metal halide perovskites and other hybrid materials.

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Fig. 1: Illustration and design of B-D phase ligands and their 2D perovskite crystal structures.
Fig. 2: Crystallographic properties of B-D phase 2D perovskites.
Fig. 3: Stability study of B-D phase 2D perovskites.
Fig. 4: Device structure and performance of the perovskite solar cells.

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Data availability

Crystallographic data for the (MeX)PbBr4 structure reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers CCDC 2426940. Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures. Source data is available in the Supplementary Files. The ω97X-D3/def2-TVZP optimized MeX, and the GFB1-xTB optimized MeXPbBr4 and MeXPbI4 geometries are available in the Supplementary Files. The other data supporting the findings of this study are available from the manuscript or its Supplementary Information. Source data are provided with this paper.

Code availability

Example simulation input scripts of SMD workflow for MeX, 2P and 4PmDA ligands and any subsequent analysis scripts are available in the Supplementary Files and from GitHub via https://github.com/Savoie-Research-Group/papers/tree/main/250922-Intralayer-Bidentate-Diammoniums-for-Stable-Two-Dimensional-Perovskites (ref. 52).

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Acknowledgements

This work is primarily supported by US Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under the Solar Energy Technologies Office Award DE-EE0009519 (L.D. and B.M.S.). S.J. and K.R.G. acknowledge funding from the National Science Foundation through DMR-2102257 (K.R.G.). This work is supported in part by the Research Instrumentation Center in the Department of Chemistry at Purdue University. The views expressed herein do not necessarily represent the views of the US Department of Energy or the US government. The authors acknowledge M. Zeller for single-crystal data collection and refinement, and X. Li and W. Shao for helpful discussions.

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Author notes

  1. These authors contributed equally: Chenjian Lin, Yuanhao Tang, Zhichen Nian.

Authors and Affiliations

  1. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, USA

    Chenjian Lin, Yuanhao Tang, Zhichen Nian, Hanjun Yang, Pengfei Wu, Yu-Ting Yang, Wenzhan Xu & Letian Dou

  2. Department of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, IN, USA

    Zhichen Nian & Brett M. Savoie

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Aidan H. Coffey, Yunfei Wang & Chenhui Zhu

  4. Department of Chemistry, Purdue University, West Lafayette, IN, USA

    Hanjun Yang & Letian Dou

  5. Department of Chemistry, University of Kentucky, Lexington, KY, USA

    Syed Joy & Kenneth R. Graham

  6. Department of Chemistry, Emory University, Atlanta, GA, USA

    Letian Dou

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Contributions

Conceptualization: C.L., B.M.S. and L.D. Synthesis, crystal growth and film studies: C.L. Heterostructure and device studies: Y.T. Computation: Z.N. and B.M.S. GIWAXS: A.H.C., Y.W. and C.Z. TRPL: H.Y. Thermogravimetric analysis/differential scanning calorimetry: P.W. PLQY: Y.-T.Y. Ultraviolet photoelectron spectroscopy: S.J. and K.R.G. Valuable discussion: W.X. Writing—original draft: C.L. and Y.T. Writing—review and editing: C.L., Y.T., Z.N., B.M.S. and L.D. Supervision: L.D.

Corresponding authors

Correspondence to Brett M. Savoie or Letian Dou.

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Competing interests

L.D., C.L. and Y.T. have filed a patent disclosure related to the B-D ligand design, synthesis and device fabrication (application number 63/906,778). The remaining authors declare no competing interests.

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Nature Chemistry thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information (download PDF )

Supplementary Materials and methods, Supplementary text, Supplementary Figs. 1–64, and Supplementary Tables 1–4.

Supplementary Video 1 (download MP4 )

SMD movie for (MeX)PbI4.

Supplementary Video 2 (download MP4 )

SMD movie for (2P)2PbI4.

Supplementary Video 3 (download MP4 )

SMD movie for (4PmDA)PbI4.

Supplementary Data (download ZIP )

Atomic coordinates for optimized structures.

Supplementary Code (download ZIP )

Simulation input scripts of SMD workflow

Source data

Source Data Fig. 2 (download XLSX )

Source data for Fig. 2e

Source Data Fig. 3 (download XLSX )

Source data for Fig. 3b and d

Source Data Fig. 4 (download XLSX )

Source data for Fig. 4b, c, d and e

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Lin, C., Tang, Y., Nian, Z. et al. Intralayer bidentate diammoniums for stable two-dimensional perovskites. Nat. Chem. 18, 275–282 (2026). https://doi.org/10.1038/s41557-025-02038-w

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