Abstract
The critical progression of structural disorder, which governs the bulk glass-forming ability (GFA), can be elucidated as an ergodicity-breaking process. Understanding the atomic characteristics involved is imperative for establishing advanced glass design principles. However, conventional glasses present significant challenges due to their inherently complex and ambiguous disorder motifs, such as intricate and random atomic clusters or ring distributions. In this work, we synthesize a family of zero-dimensional hybrid metal halides with tunable short- to medium-range structural arrangements to form glasses with diverse GFAs. Through altering molecular shape and surface electrostatic potential of organic cations, their rotational order is able to be broken in a controlle…
Abstract
The critical progression of structural disorder, which governs the bulk glass-forming ability (GFA), can be elucidated as an ergodicity-breaking process. Understanding the atomic characteristics involved is imperative for establishing advanced glass design principles. However, conventional glasses present significant challenges due to their inherently complex and ambiguous disorder motifs, such as intricate and random atomic clusters or ring distributions. In this work, we synthesize a family of zero-dimensional hybrid metal halides with tunable short- to medium-range structural arrangements to form glasses with diverse GFAs. Through altering molecular shape and surface electrostatic potential of organic cations, their rotational order is able to be broken in a controlled manner. This leads to distinct phase space partitions of molecular movements, allowing for tunable GFAs. Our findings provide a fundamental design approach for synthesizing property-oriented glasses by controlling molecular rotational order, which can be applicable to a wide range of molecular glasses and amorphous solids.
Data availability
All data are available in the Article or its Supplementary information, and available from the corresponding authors upon request. The raw data have been deposited in a Figshare repository (https://doi.org/10.6084/m9.figshare.30880172). Source data are provided with this paper.
References
Angell, C. A. Formation of glasses from liquids and biopolymers. Science267, 1924–1935 (1995).
Debenedetti, P. G. & Stillinger, F. H. Supercooled liquids and the glass transition. Nature410, 259–267 (2001).
Kennedy, D. & Norman, C. What don’t we know? Science309, 75 (2005).
Santen, L. & Krauth, W. Absence of thermodynamic phase transition in a model glass former. Nature405, 550–551 (2000).
Greaves, G. N. & Sen, S. Inorganic glasses, glass-forming liquids and amorphizing solids. *Adv. Phys.*56, 1–166 (2007).
Bennett, T. D. et al. Structure and properties of an amorphous metal-organic framework. *Phys. Rev. Lett.*104, 115503 (2010).
Yang, Y. et al. Determining the three-dimensional atomic structure of an amorphous solid. Nature592, 60–64 (2021).
Swallen, S. F. et al. Organic glasses with exceptional thermodynamic and kinetic stability. Science315, 353–356 (2007).
Ma, N. & Horike, S. Metal-organic network-forming glasses. *Chem. Rev.*122, 4163–4203 (2022).
Liu, L. R. et al. Ergodicity breaking in rapidly rotating C60 fullerenes. Science381, 778–783 (2023).
Thirumalai, D., Mountain, R. D. & Kirkpatrick, T. R. Ergodic behavior in supercooled liquids and in glasses. Phys. Rev. A39, 3563–3574 (1989).
Hedges, L. O., Jack, R. L., Garrahan, J. P. & Chandler, D. Dynamic order-disorder in atomistic models of structural glass formers. Science323, 1309–1313 (2009).
Stillinger, F. H. & Debenedetti, P. G. Glass transition thermodynamics and kinetics. *Annu. Rev. Condens. Matter Phys.*4, 263–285 (2013).
Ma, E. Tuning order in disorder. *Nat. Mater.*14, 547–552 (2015).
Frankberg, E. J. et al. Highly ductile amorphous oxide at room temperature and high strain rate. Science366, 864–869 (2019).
Wang, W. H. The elastic properties, elastic models and elastic perspectives of metallic glasses. *Prog. Mater. Sci.*57, 487–656 (2012).
Fang, W. et al. Organic-inorganic covalent-ionic molecules for elastic ceramic plastic. Nature619, 293–299 (2023).
Yang, Z. et al. ZIF-62 glass foam self-supported membranes to address CH4/N2 separations. *Nat. Mater.*22, 888–894 (2023).
Chen, Y. et al. Microscopic ergodicity breaking governs the emergence and evolution of elasticity in glass-forming nanoclay suspensions. Phys. Rev. E102, 042619 (2020).
Rino, J. P. et al. Structure of rings in vitreous SiO2. Phys. Rev. B47, 3053–3062 (1993).
Salmon, P. S., Martin, R. A., Mason, P. E. & Cuello, G. J. Topological versus chemical ordering in network glasses at intermediate and extended length scales. Nature435, 75–78 (2005).
Zhou, Q. et al. Experimental method to quantify the ring size distribution in silicate glasses and simulation validation thereof. *Sci. Adv.*7, eabh1761 (2021).
Inoue, A. Stabilization of metallic supercooled liquid and bulk amorphous alloys. *Acta Mater.*48, 279–306 (2000).
Sheng, H. W. et al. Atomic packing and short-to-medium-range order in metallic glasses. Nature439, 419–425 (2006).
Li, M.-X. et al. Data-driven discovery of a universal indicator for metallic glass forming ability. *Nat. Mater.*21, 165–172 (2021).
Wrighton, M. & Ginley, D. Excited state decay of tetrahalomanganese(II) complexes. *Chem. Phys.*4, 295–299 (1974).
Balsamy, S., Natarajan, P., Vedalakshmi, R. & Muralidharan, S. Triboluminescence and vapor-induced phase transitions in the solids of methyltriphenylphosphonium tetrahalomanganate(II) complexes. *Inorg. Chem.*53, 6054–6059 (2014).
Li, M. & Xia, Z. Recent progress of zero-dimensional luminescent metal halides. *Chem. Soc. Rev.*50, 2626–2662 (2021).
Luo, J. B. et al. A melt-quenched luminescent glass of an organic–inorganic manganese halide as a large-area scintillator for radiation detection. *Angew. Chem. Int. Ed.*62, e202216504 (2023).
Xu, L.-J. et al. Green-light-emitting diodes based on tetrabromide manganese(II) complex through solution process. *Adv. Mater.*29, 1605739 (2017).
Dove, M. T. & Li, G. Review: pair distribution functions from neutron total scattering for the study of local structure in disordered materials. *Nucl. Anal.*1, 100037 (2022).
Selinger, J. V. Introduction to the Theory of Soft Matter: From Ideal Gases to Liquid Crystals, Ch. 5 (Springer, 2016). 1.
Zheng, Q. et al. Understanding glass through differential scanning calorimetry. *Chem. Rev.*119, 7848–7939 (2019).
Turnbull, D. Under what conditions can a glass be formed? *Contem. Phys.*10, 473–488 (1969).
Kissinger, H. E. Reaction kinetics in differential thermal analysis. *Anal. Chem.*29, 1702–1706 (1957).
Moynihan, C. T., Easteal, A. J., Wilder, J. & Tucker, J. Dependence of the glass transition temperature on heating and cooling rate. *J. Phys. Chem.*78, 2673–2677 (1974).
Vyazovkin, S. Kissinger method in kinetics of materials: things to beware and be aware of. Molecules25, 2813 (2020).
Yin, M. et al. Crystal–glass phase transition enabling reversible fluorescence switching in zero-dimensional antimony halides. *Chem. Commun.*59, 11361–11364 (2023).
Zhang, Z.-Z. et al. Organic–inorganic hybrid Mn-based transparent glass for curved X-ray scintillation imaging. *Adv. Opt. Mater.*12, 2302434 (2024).
Dong, C. et al. Organic–inorganic hybrid glasses of atomically precise nanoclusters. *J. Am. Chem. Soc.*146, 7373–7385 (2024).
Feng, T. et al. Large-area transparent antimony-based perovskite glass for high-resolution X-ray imaging. ACS Nano18, 16715–16725 (2024).
He, Z.-L. et al. A universal strategy toward two-component organic–inorganic metal-halide luminescent glasses and glass–crystal composites. *Sci. Adv.*11, eadu1982 (2025).
Hutter, J., Iannuzzi, M., Schiffmann, F. & VandeVondele, J. CP2K: atomistic simulations of condensed matter systems. *Wiley Interdiscip. Rev.-Comput. Mol. Sci.*4, 15–25 (2014).
Abraham, M. J. et al. GROMACS: high performance molecular simulations through multi-level parallelism from laptops to supercomputers. SoftwareX1–2, 19–25 (2015).
Bussi, G. & Laio, A. Using metadynamics to explore complex free-energy landscapes. *Nat. Rev. Phys.*2, 200–212 (2020).
Pearson, K. Note on regression and inheritance in the case of two parents. *Proc. R. Soc. Lond.*58, 240–242 (1895).
Spearman, C. The proof and measurement of association between two things. *Am. J. Psychol.*15, 72–101 (1904).
de Siqueira Santos, S., Takahashi, D. Y., Nakata, A. & Fujita, A. A comparative study of statistical methods used to identify dependencies between gene expression signals. *Brief Bioinform.*15, 906–918 (2014).
Lu, T. & Chen, F. Multiwfn: a multifunctional wavefunction analyzer. *J. Comput. Chem.*33, 580–592 (2012).
Neese, F., Wennmohs, F., Becker, U. & Riplinger, C. The ORCA quantum chemistry program package. *J. Chem. Phys.*152, 224108 (2020).
Neese, F. Software update: the ORCA program system—Version 5.0. *Wiley Interdiscip. Rev.-Comput. Mol. Sci.*12, e1606 (2022).
Murray, J. S. & Politzer, P. Statistical analysis of the molecular surface electrostatic potential: an approach to describing noncovalent interactions in condensed phases. *J. Mol. Struc-Theochem.*425, 107–114 (1998).
Lin, J. et al. Narrowing the band of green emission in manganese hybrids by reducing the hydrogen bond strength and structural distortion. J. Mater. Chem. C10, 16773–16780 (2022).
Li, B. et al. Zero-dimensional luminescent metal halide hybrids enabling bulk transparent medium as large-area X-ray scintillators. *Adv. Opt. Mater.*10, 2102793 (2022).
Dolomanov, O. V. et al. OLEX2: a complete structure solution, refinement and analysis program. *J. Appl. Crystallogr.*42, 339–341 (2009).
Qiu, X., Thompson, J. W. & Billinge, S. J. L. PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data. *J. Appl. Crystallogr.*37, 678–678 (2004).
Tucker, M. G. et al. RMCProfile: reverse Monte Carlo for polycrystalline materials. J. Phys.-Condes. Matter19, 335218 (2007).
Adamo, C. & Barone, V. Toward reliable density functional methods without adjustable parameters: the PBE0 model. *J. Chem. Phys.*110, 6158–6170 (1999).
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).
Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. *J. Chem. Phys.*132, 154104 (2010).
Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. *J. Comput. Chem.*32, 1456–1465 (2011).
Papajak, E. et al. Perspectives on basis sets beautiful: seasonal plantings of diffuse basis functions. *J. Chem. Theory Comput.*7, 3027–3034 (2011).
Martínez, L., Andrade, R., Birgin, E. G. & Martínez, J. M. PACKMOL: a package for building initial configurations for molecular dynamics simulations. *J. Comput. Chem.*30, 2157–2164 (2009).
Lu T. Sobtop, Version 1.0 (dev3.1). http://sobereva.com/soft/Sobtop. 1.
Wang, J., Wang, W., Kollman, P. A. & Case, D. A. Automatic atom type and bond type perception in molecular mechanical calculations. *J. Mol. Graph.*25, 247–260 (2006).
Wang, J. et al. Development and testing of a general amber force field. *J. Comput. Chem.*25, 1157–1174 (2004).
Humphrey, W., Dalke, A. & Schulten, K. VMD: visual molecular dynamics. *J. Mol. Graph.*14, 33–38 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. *Phys. Rev. Lett.*77, 3865–3868 (1996).
Goedecker, S., Teter, M. & Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B54, 1703–1710 (1996).
Grimme, S., Bannwarth, C. & Shushkov, P. A robust and accurate tight-binding quantum chemical method for structures, vibrational frequencies, and noncovalent interactions of large molecular systems parametrized for all spd-block elements (Z = 1-86). *J. Chem. Theory Comput.*13, 1989–2009 (2017).
Elstner, M. et al. Self-consistent-charge density-functional tight-binding method for simulations of complex materials properties. Phys. Rev. B58, 7260–7268 (1998).
Cui, M., Reuter, K. & Margraf, J. T. Obtaining robust density functional tight-binding parameters for solids across the periodic table. *J. Chem. Theory Comput.*20, 5276–5290 (2024).
Bonomi, M. et al. PLUMED: a portable plugin for free-energy calculations with molecular dynamics. *Comput. Phys. Commun.*180, 1961–1972 (2009).
Acknowledgements
We acknowledge the financial support from the National Key Research and Development Program of China (No. 2022YFA1503301 to W.L.), the National Natural Science Foundation of China (Nos. 22035003 to X.H.B., 22375105 to W.L., and 12174274 to M.T.D.), and the State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology (No. SYSJJ2022-02 to W.L.).
Author information
Author notes
These authors contributed equally: Zi-Ying Li, Rui Feng.
Authors and Affiliations
School of Materials Science and Engineering, Nankai University & TKL of Metal and Molecule Based Material Chemistry, Tianjin, China
Zi-Ying Li, Rui Feng, Zhi-Gang Li, Shi-Shuang Huang, Ze Chang, Wei Li & Xian-He Bu 1.
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, China
Martin T. Dove 1.
School of Physical and Chemical Sciences, Queen Mary University of London, London, UK
Martin T. Dove 1.
Institute of Materials Research and Engineering, Agency for Science, Technology and Research, Singapore, Singapore
Fengxia Wei 1.
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, China
Caijuan Shi, Lirong Zheng & Xiaodong Li 1.
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, China
Neng Li
Authors
- Zi-Ying Li
- Rui Feng
- Zhi-Gang Li
- Martin T. Dove
- Shi-Shuang Huang
- Fengxia Wei
- Caijuan Shi
- Ze Chang
- Neng Li
- Lirong Zheng
- Xiaodong Li
- Wei Li
- Xian-He Bu
Contributions
Z.-Y.L., R.F., W.L., and X.-H.B. conceived the idea and led the research. Z.-Y.L. and R.F. contributed equally to this work. Z.-Y.L. and R.F. performed the experiments and collected the data. Z.-Y.L. synthesized the materials and performed XRD, SEM, FTIR, PL, polarization, DSC, TGA, and Raman tests. R.F. performed some PL, FTIR, and Raman tests. R.F. performed the theoretical calculations. C.S., X.L., and L.Z. performed X-ray total scattering measurements. W.L., X.-H.B., Z.C., Z.-Y.L., R.F., M.T.D., N.L., and Z.-G.L. evaluated and discussed data. Z.-Y.L., R.F., F.W., W.L., and X.-H.B. contributed to writing the manuscript. S.-S.H. helped to revise the manuscript. All authors reviewed and discussed the manuscript.
Corresponding authors
Correspondence to Rui Feng, Wei Li or Xian-He Bu.
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Li, ZY., Feng, R., Li, ZG. et al. Glass formation in hybrid metal halides via breaking molecular rotational order. Nat Commun (2026). https://doi.org/10.1038/s41467-026-68563-5
Received: 14 November 2024
Accepted: 06 January 2026
Published: 22 January 2026
DOI: https://doi.org/10.1038/s41467-026-68563-5