Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Synthesis of zero-dimensional octahedral metal halides through solvent incorporation and their photophysical properties

Nature Chemistry volume 17, pages 1401–1409 (2025)Cite this article

Subjects

Abstract

Zero-dimensional (0D) metal halides, which feature discrete metal halide octahedra interspersed with large organoammonium cations, are the building blocks of halide perovskites. The optical properties of these materials make them promising candidates in light-emitting devices. However, developing their general design principles remains challenging. Here we report an antisolvent incorporation approach that transforms a broad range of two-dimensional tin iodide perovskites into 0D structures. This approach accommodates diverse organic cations and antisolvent molecules and is extendable to germanium and lead analogues. We show that enhancing the structural rigidity in Sn-based octahedra—modulated by organic packing—increases the radiative recombination rate while decreasing the non-radiative recombination rate, achieving near-unity photoluminescence quantum yield. Ge- and Sn-based structures exhibit large Stokes shifts and microsecond-scale triplet lifetimes due to localized excited states, while their Pb-based counterpart shows faster recombination via triplet–singlet mixing, supported by theoretical calculations. This work offers a versatile synthetic platform for 0D metal halides and deepens our current understanding of excited-state dynamics in halide perovskites.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to the full article PDF.

USD 39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Rational synthesis and molecular design of 0D metal halides.
Fig. 2: Structural properties of 0D Sn-based structures.
Fig. 3: Photophysical properties of 0D Sn-based structures and their correlations with structural properties.
Fig. 4: Photophysical properties of 0D structures with varying metal cations.
Fig. 5: Excited-state structural relaxation of 0D metal halides.

Similar content being viewed by others

Data availability

Data that support the finding of this study can be found in the article or its Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2370156 (A1), 2370157 (A2), 2370158 (A3), 2370159 (A4), 2370160 (A5), 2370161 (A6), 2370162 (A7), 2370163 (A8), 2370164 (A9), 2370165 (A10), 2370166 (A13), 2370167 (B2), 2370168 (B5), 2370169 (B6), 2370170 (C1), 2370171 [(PEA)6GeI8(Bz)2], 2370172 [(PEA)6PbI8(Bz)2], 2370173 [(PEA)6PbI8(CBz)2], 2370174 [(PEA)6PbI8(DCB)2], 2420403 (A12), 2420404 (A11), 2420405 (B1), 2420406 (B3) and 2420407 (B4). Copies of the data can be obtained free of charge at https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

References

  1. Fu, Y. et al. Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties. Nat. Rev. Mater. 4, 169–188 (2019).

    Article  CAS  Google Scholar 

  2. Akkerman, Q. A. & Manna, L. What defines a halide perovskite? ACS Energy Lett. 5, 604–610 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  3. Lin, H., Zhou, C., Tian, Y., Siegrist, T. & Ma, B. Low-dimensional organometal halide perovskites. ACS Energy Lett. 3, 54–62 (2018).

    Article  CAS  Google Scholar 

  4. Yakunin, S. et al. High-resolution remote thermometry and thermography using luminescent low-dimensional tin-halide perovskites. Nat. Mater. 18, 846–852 (2019).

    Article  CAS  PubMed  Google Scholar 

  5. Ju, Y. et al. Water-sensitive mixed-phase PEA6SnI8 perovskite derivative single crystal for humidity detection. Cryst. Growth Des. 22, 4689–4695 (2022).

    Article  CAS  Google Scholar 

  6. Zhou, C. et al. Highly efficient broadband yellow phosphor based on zero-dimensional tin mixed-halide perovskite. ACS Appl. Mater. Interfaces 9, 44579–44583 (2017).

    Article  CAS  PubMed  Google Scholar 

  7. Wang, Y. et al. Room temperature ferroelectricity and blue photoluminescence in zero dimensional organic lead iodine perovskites. J. Mater. Chem. C 9, 223–227 (2021).

    Article  CAS  Google Scholar 

  8. Li, Z. et al. Precursor tailoring enables alkylammonium tin halide perovskite phosphors for solid‐state lighting. Adv. Funct. Mater. 32, 2111346 (2022).

    Article  CAS  Google Scholar 

  9. Xu, L.-J. et al. 0D and 2D: the cases of phenylethylammonium tin bromide hybrids. Chem. Mater. 32, 4692–4698 (2020).

    Article  CAS  Google Scholar 

  10. Cui, B.-B. et al. Locally collective hydrogen bonding isolates lead octahedra for white emission improvement. Nat. Commun. 10, 5190 (2019).

    Article  PubMed  PubMed Central  Google Scholar 

  11. Jia, X. et al. Methylpiperazine based 0D chiral hybrid lead halides for second harmonic generation. Dalton Trans. 51, 7248–7254 (2022).

    Article  CAS  PubMed  Google Scholar 

  12. Zhang, L. et al. Organic cation-directed modulation of emissions in zero-dimensional hybrid tin bromides. Inorg. Chem. 61, 14857–14863 (2022).

    Article  CAS  PubMed  Google Scholar 

  13. Fu, P. et al. Organic-inorganic layered and hollow tin bromide perovskite with tunable broadband emission. ACS Appl. Mater. Interfaces 10, 34363–34369 (2018).

    Article  CAS  PubMed  Google Scholar 

  14. Weber, O. J., Marshall, K. L., Dyson, L. M. & Weller, M. T. Structural diversity in hybrid organic-inorganic lead iodide materials. Acta Cryst. 71, 668–678 (2015).

    CAS  Google Scholar 

  15. Sun, C. et al. A zero-dimensional hybrid lead perovskite with highly efficient blue-violet light emission. J. Mater. Chem. C 8, 11890–11895 (2020).

    Article  CAS  Google Scholar 

  16. Benin, B. M. et al. Highly emissive self-trapped excitons in fully inorganic zero-dimensional tin halides. Angew. Chem. Int. Ed. 57, 11329–11333 (2018).

    Article  CAS  Google Scholar 

  17. Zheng, D.-S. et al. Highly emissive 0D Tin(II) hybrid for white LED. J. Lumin. 270, 120530 (2024).

    Article  CAS  Google Scholar 

  18. Nikl, M. et al. Photoluminescence of Cs4PbBr6 crystals and thin films. Chem. Phys. Lett. 306, 280–284 (1999).

    Article  CAS  Google Scholar 

  19. Huang, X. et al. Understanding electron–phonon interactions in 3D lead halide perovskites from the stereochemical expression of 6s2 lone pairs. J. Am. Chem. Soc. 144, 12247–12260 (2022).

    Article  CAS  PubMed  Google Scholar 

  20. Miyata, K., Atallah, T. L. & Zhu, X.-Y. Lead halide perovskites: crystal–liquid duality, phonon glass electron crystals, and large polaron formation. Sci. Adv. 3, e1701469 (2017).

    Article  PubMed  PubMed Central  Google Scholar 

  21. Ghosh, D., Welch, E., Neukirch, A. J., Zakhidov, A. & Tretiak, S. Polarons in halide perovskites: a perspective. J. Phys. Chem. Lett. 11, 3271–3286 (2020).

    Article  CAS  PubMed  Google Scholar 

  22. Gong, X. et al. Electron–phonon interaction in efficient perovskite blue emitters. Nat. Mater. 17, 550–556 (2018).

    Article  CAS  PubMed  Google Scholar 

  23. Becker, M. A. et al. Bright triplet excitons in caesium lead halide perovskites. Nature 553, 189–193 (2018).

    Article  CAS  PubMed  Google Scholar 

  24. Even, J., Pedesseau, L., Jancu, J.-M. & Katan, C. Importance of spin–orbit coupling in hybrid organic/inorganic perovskites for photovoltaic applications. J. Phys. Chem. Lett. 4, 2999–3005 (2013).

    Article  CAS  Google Scholar 

  25. Gu, J. & Fu, Y. Is there an optimal spacer cation for two-dimensional lead iodide perovskites? ACS Mater. Au 5, 24–34 (2025).

    Article  CAS  PubMed  Google Scholar 

  26. Mao, L., Stoumpos, C. C. & Kanatzidis, M. G. Two-dimensional hybrid halide perovskites: principles and promises. J. Am. Chem. Soc. 141, 1171–1190 (2019).

    Article  CAS  PubMed  Google Scholar 

  27. Park, J. Y. et al. Thickness control of organic semiconductor-incorporated perovskites. Nat. Chem. 15, 1745–1753 (2023).

    Article  CAS  PubMed  Google Scholar 

  28. Yaffe, O. et al. Local polar fluctuations in lead halide perovskite crystals. Phys. Rev. Lett. 118, 136001 (2017).

    Article  PubMed  Google Scholar 

  29. Wang, X. & Yan, Y. in Hybrid Organic Inorganic Perovskites (ed. Vardeny, Z. V.) Ch. 2, 37–63 (World Scientific Publishing, 2022).

  30. Ranfagni, A., Mugnai, D., Bacci, M., Viliani, G. & Fontana, M. P. The optical properties of thallium-like impurities in alkali-halide crystals. Adv. Phys. 32, 823–905 (1983).

    Article  CAS  Google Scholar 

  31. Li, X. et al. Optical bandgap anomaly with tuning dimensionality in germanium perovskites: interplay between quantum confinement and lone pair expression. Chem 10, 891–909 (2024).

    Article  CAS  Google Scholar 

  32. Li, X., Guan, Y., Li, X. & Fu, Y. Stereochemically active lone pairs and nonlinear optical properties of two-dimensional multilayered tin and germanium iodide perovskites. J. Am. Chem. Soc. 144, 18030–18042 (2022).

    Article  CAS  PubMed  Google Scholar 

  33. Lü, X. et al. Regulating off-centering distortion maximizes photoluminescence in halide perovskites. Natl Sci. Rev. 8, nwaa288 (2020).

    Article  PubMed  PubMed Central  Google Scholar 

  34. Stoumpos, C. C. et al. Hybrid germanium iodide perovskite semiconductors: active lone pairs, structural distortions, direct and indirect energy gaps, and strong nonlinear optical properties. J. Am. Chem. Soc. 137, 6804–6819 (2015).

    Article  CAS  PubMed  Google Scholar 

  35. Wu, X. et al. Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites. Sci. Adv. 3, e1602388 (2017).

    Article  PubMed  PubMed Central  Google Scholar 

  36. Srimath Kandada, A. R. & Silva, C. Exciton polarons in two-dimensional hybrid metal-halide perovskites. J. Phys. Chem. Lett. 11, 3173–3184 (2020).

    Article  CAS  PubMed  Google Scholar 

  37. Hansen, K. R. et al. Low exciton binding energies and localized exciton–polaron states in 2D tin halide perovskites. Adv. Opt. Mater. 10, 2102698 (2022).

    Article  CAS  Google Scholar 

  38. Mahata, A., Meggiolaro, D. & De Angelis, F. From large to small polarons in lead, tin, and mixed lead–tin halide perovskites. J. Phys. Chem. Lett. 10, 1790–1798 (2019).

    Article  CAS  PubMed  Google Scholar 

  39. Ouhbi, H., Ambrosio, F., De Angelis, F. & Wiktor, J. Strong electron localization in tin halide perovskites. J. Phys. Chem. Lett. 12, 5339–5343 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  40. Shao, W. et al. Molecular templating of layered halide perovskite nanowires. Science 384, 1000–1006 (2024).

    Article  CAS  PubMed  Google Scholar 

  41. Li, Y. et al. Phase-pure 2D tin halide perovskite thin flakes for stable lasing. Sci. Adv. 9, eadh0517 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  42. Han, D. et al. Tautomeric mixture coordination enables efficient lead-free perovskite LEDs. Nature 622, 493–498 (2023).

    Article  CAS  PubMed  Google Scholar 

  43. Baryshnikov, G., Minaev, B. & Ågren, H. Theory and calculation of the phosphorescence phenomenon. Chem. Rev. 117, 6500–6537 (2017).

    Article  CAS  PubMed  Google Scholar 

  44. Wright, A. D. et al. Electron–phonon coupling in hybrid lead halide perovskites. Nat. Commun. 7, 11755 (2016).

    Article  Google Scholar 

  45. Parrott, E. S. et al. Effect of structural phase transition on charge-carrier lifetimes and defects in CH3NH3SnI3 perovskite. J. Phys. Chem. Lett. 7, 1321–1326 (2016).

    Article  CAS  PubMed  Google Scholar 

  46. Sousa, C., Tosoni, S. & Illas, F. Theoretical approaches to excited-state-related phenomena in oxide surfaces. Chem. Rev. 113, 4456–4495 (2013).

    Article  CAS  PubMed  Google Scholar 

  47. Kolafa, J. & Perram, J. W. Cutoff errors in the Ewald summation formulae for point charge systems. Mol. Simul. 9, 351–368 (1992).

    Article  CAS  Google Scholar 

  48. Frisch, M. Gaussian 09, Revision d. 01, Gaussian (Gaussian, 2009).

  49. Schäfer, A., Horn, H. & Ahlrichs, R. Fully optimized contracted Gaussian basis sets for atoms Li to Kr. J. Chem. Phys. 97, 2571–2577 (1992).

    Article  Google Scholar 

  50. Weigend, F. & Ahlrichs, R. Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy. Phys. Chem. Chem. Phys. 7, 3297–3305 (2005).

    Article  CAS  PubMed  Google Scholar 

  51. Eichkorn, K., Weigend, F., Treutler, O. & Ahlrichs, R. Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials. Theor. Chem. Acta 97, 119–124 (1997).

    Article  CAS  Google Scholar 

  52. Binkley, J. S., Pople, J. A. & Hehre, W. J. Self-consistent molecular orbital methods. 21. Small split-valence basis sets for first-row elements. J. Am. Chem. Soc. 102, 939–947 (1980).

    Article  CAS  Google Scholar 

  53. Gordon, M. S., Binkley, J. S., Pople, J. A., Pietro, W. J. & Hehre, W. J. Self-consistent molecular-orbital methods. 22. Small split-valence basis sets for second-row elements. J. Am. Chem. Soc. 104, 2797–2803 (1982).

    Article  CAS  Google Scholar 

  54. Dobbs, K. D. & Hehre, W. J. Molecular orbital theory of the properties of inorganic and organometallic compounds 4. Extended basis sets for third‐and fourth‐row, main‐group elements. J. Comput. Chem. 7, 359–378 (1986).

    Article  CAS  Google Scholar 

  55. Metz, B., Stoll, H. & Dolg, M. Small-core multiconfiguration-Dirac–Hartree–Fock-adjusted pseudopotentials for post-d main group elements: application to PbH and PbO. J. Chem. Phys. 113, 2563–2569 (2000).

    Article  CAS  Google Scholar 

  56. Peterson, K. A., Figgen, D., Goll, E., Stoll, H. & Dolg, M. Systematically convergent basis sets with relativistic pseudopotentials. II. Small-core pseudopotentials and correlation consistent basis sets for the post-d group 16–18 elements. J. Chem. Phys. 119, 11113–11123 (2003).

    Article  CAS  Google Scholar 

  57. Perdew, J. P., Ernzerhof, M. & Burke, K. Rationale for mixing exact exchange with density functional approximations. J. Chem. Phys. 105, 9982–9985 (1996).

    Article  CAS  Google Scholar 

  58. Neese, F. The ORCA program system. WIREs Comput. Mol. Sci. 2, 73–78 (2012).

    Article  CAS  Google Scholar 

  59. Neese, F. Software update: the ORCA program system—version 5.0. WIREs Comput. Mol. Sci. 12, e1606 (2022).

    Article  Google Scholar 

  60. Neese, F., Wennmohs, F., Hansen, A. & Becker, U. Efficient, approximate and parallel Hartree–Fock and hybrid DFT calculations. A ‘chain-of-spheres’ algorithm for the Hartree–Fock exchange. Chem. Phys. 356, 98–109 (2009).

    Article  CAS  Google Scholar 

  61. Douglas, M. & Kroll, N. M. Quantum electrodynamical corrections to the fine structure of helium. Ann. Phys. 82, 89–155 (1974).

    Article  CAS  Google Scholar 

  62. Hess, B. A. Applicability of the no-pair equation with free-particle projection operators to atomic and molecular structure calculations. Phys. Rev. A 32, 756–763 (1985).

    Article  CAS  Google Scholar 

  63. Hess, B. A. Relativistic electronic-structure calculations employing a two-component no-pair formalism with external-field projection operators. Phys. Rev. A 33, 3742–3748 (1986).

    Article  CAS  Google Scholar 

  64. Neese, F. Efficient and accurate approximations to the molecular spin–orbit coupling operator and their use in molecular g-tensor calculations. J. Chem. Phys. 122, 034107 (2005).

    Article  Google Scholar 

  65. Heß, B. A., Marian, C. M., Wahlgren, U. & Gropen, O. A mean-field spin–orbit method applicable to correlated wavefunctions. Chem. Phys. Lett. 251, 365–371 (1996).

    Article  Google Scholar 

  66. Camiletti, G. G., Machado, S. F. & Jorge, F. E. Gaussian basis set of double zeta quality for atoms K through Kr: application in DFT calculations of molecular properties. J. Comput. Chem. 29, 2434–2444 (2008).

    Article  CAS  PubMed  Google Scholar 

  67. Barros, C. L., De Oliveira, P. J. P., Jorge, F. E., Canal Neto, A. & Campos, M. Gaussian basis set of double zeta quality for atoms Rb through Xe: application in non-relativistic and relativistic calculations of atomic and molecular properties. Mol. Phys. 108, 1965–1972 (2010).

    Article  CAS  Google Scholar 

  68. Canal Neto, A. & Jorge, F. E. All-electron double zeta basis sets for the most fifth-row atoms: application in DFT spectroscopic constant calculations. Chem. Phys. Lett. 582, 158–162 (2013).

    Article  CAS  Google Scholar 

  69. Canal Neto, A., Muniz, E. P., Centoducatte, R. & Jorge, F. E. Gaussian basis sets for correlated wave functions. Hydrogen, helium, first- and second-row atoms. J. Mol. Struct. THEOCHEM 718, 219–224 (2005).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work is supported by the National Natural Science Foundation of China (grant numbers 22071003 to Z.L., 22271006 to Y.F., 12234001 to H.J., 61935016 to Z.B. and 92156016 to Z.L.), the National Key Research and Development Program of China (grant numbers 2022YFB3503702 to Z.L. and 2023YFB3506901 to Z.L.) and the Li Ge-Zhao Ning Youth Research Foundation (grant number LGZNQN202402 to Y.F.). We acknowledge the high-performance computing (HPC) platform of Peking University and Beijing Super Computing Center (BSCC) for providing HPC resources for the quantum-chemical calculations. The measurements of SCXRD and all the PL spectra in Edinburgh Instruments’ FLS980 PL spectrometer were performed at the Analytical Instrumentation Center of Peking University, with the help of J. Su and M. Chen, respectively.

Author information

Author notes

  1. These authors contributed equally: Nanlong Zheng, Songqi Cao.

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Nanlong Zheng, Songqi Cao, Tianhao Zhang, Peihao Huo, Conglan Hu, Huanyu Liu, Ruoyao Guo, Wenchao Yan, Jiayin Zheng, Xiaofan Jiang, Zhenyu Zhu, Junliang Sun, Hong Jiang, Zuqiang Bian, Yongping Fu & Zhiwei Liu

Authors
  1. Nanlong Zheng
    View author publications

    Search author on:PubMed Google Scholar

  2. Songqi Cao
    View author publications

    Search author on:PubMed Google Scholar

  3. Tianhao Zhang
    View author publications

    Search author on:PubMed Google Scholar

  4. Peihao Huo
    View author publications

    Search author on:PubMed Google Scholar

  5. Conglan Hu
    View author publications

    Search author on:PubMed Google Scholar

  6. Huanyu Liu
    View author publications

    Search author on:PubMed Google Scholar

  7. Ruoyao Guo
    View author publications

    Search author on:PubMed Google Scholar

  8. Wenchao Yan
    View author publications

    Search author on:PubMed Google Scholar

  9. Jiayin Zheng
    View author publications

    Search author on:PubMed Google Scholar

  10. Xiaofan Jiang
    View author publications

    Search author on:PubMed Google Scholar

  11. Zhenyu Zhu
    View author publications

    Search author on:PubMed Google Scholar

  12. Junliang Sun
    View author publications

    Search author on:PubMed Google Scholar

  13. Hong Jiang
    View author publications

    Search author on:PubMed Google Scholar

  14. Zuqiang Bian
    View author publications

    Search author on:PubMed Google Scholar

  15. Yongping Fu
    View author publications

    Search author on:PubMed Google Scholar

  16. Zhiwei Liu
    View author publications

    Search author on:PubMed Google Scholar

Contributions

N.Z. and Y.F. conceived the idea. N.Z. designed the experiments. N.Z. synthesized and characterized the crystals with the help of C.H., H.L., J.Z., R.G. and W.Y. N.Z., X.J., T.Z., Z.Z. and J.S. solved the single-crystal structures. S.C. and H.J. performed the theoretical calculations. T.Z. performed the low-frequency Raman measurements. P.H. performed the stability tests. Z.L., Y.F., Z.B. and H.J. supervised the project. N.Z. and Y.F. wrote the paper with input of the theoretical part from S.C. All authors have interpreted the findings, revised the paper and approved the final version.

Corresponding authors

Correspondence to Hong Jiang, Zuqiang Bian, Yongping Fu or Zhiwei Liu.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

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

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Extended Data Fig. 1 0D metal halides prepared in this study.

The figure depicts the crystal structure of the compounds along with their symbol and colour coding.

Supplementary information

Supplementary Information (download PDF )

Supplementary Tables 1–8, Figs. 1–24, CheckCIF information and Discussion.

Supplementary Data 1 (download ZIP )

Atomic coordinates of optimized computational models.

Source data

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zheng, N., Cao, S., Zhang, T. et al. Synthesis of zero-dimensional octahedral metal halides through solvent incorporation and their photophysical properties. Nat. Chem. 17, 1401–1409 (2025). https://doi.org/10.1038/s41557-025-01869-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Version of record:

  • Issue date:

  • DOI: https://doi.org/10.1038/s41557-025-01869-x

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing