Abstract
The development of high-performance organic ferromagnetic semiconductors has been hampered by the intrinsic coupling of radical formation and structural organization during synthesis, which makes it difficult to achieve long-range magnetic coupling in highly conjugated systems. Here, we report an effective topochemical reduction strategy that decouples radical formation from structural organization, enabling unprecedented control over intermolecular arrangements in organic ferromagnetic materials. Using perylene diimide as a model system, this approach preserves the highly ordered structure of thermally evaporated precursor films during reduction, resulting in a shortened π-π stacking distance of 3.26 Å and exceptional long-range molecular order. The resulting films exhibit remarkable room-temperature ferromagnetism, as evidenced by X-ray magnetic circular dichroism, with a saturation magnetization of 10.5 emu g⁻1—nearly an order of magnitude higher than conventional organic magnetic materials—while retaining semiconducting properties. Generality of this strategy has also been demonstrated in naphthalene-based systems, underscoring its broad applicability. Theoretical calculations reveal that this enhanced performance originates from optimized ferromagnetic coupling between adjacent radicals through controlled twisted stacking configurations. This work provides a practical route to high-performance ferromagnetic semiconductors.
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References
Shen, A. et al. (Ga, Mn)As/GaAs diluted magnetic semiconductor superlattice structures prepared by molecular beam epitaxy. Jpn. J. Appl. Phys. 36, L73 (1997).
Zhao, K. et al. New diluted ferromagnetic semiconductor with Curie temperature up to 180 K and isostructural to the ‘122’ iron-based superconductors. Nat. Commun. 4, 1442 (2013).
Kong, D. et al. Emerging two-dimensional ferromagnetic semiconductors. Chem. Soc. Rev. 53, 11228–11250 (2024).
Wang, L. et al. Intercalated architecture of MA2Z4 family layered van der Waals materials with emerging topological, magnetic and superconducting properties. Nat. Commun. 12, 2361 (2021).
McConnell, H. M. Ferromagnetism in Solid Free Radicals. J. Chem. Phys. 39, 1910–1910 (1963).
Takahashi, M. et al. Discovery of a quasi-1D organic ferromagnet, p-NPNN. Phys. Rev. Lett. 67, 746–748 (1991).
Tuček, J. et al. Room temperature organic magnets derived from sp3 functionalized graphene. Nat. Commun. 8, 14525 (2017).
Li, T. et al. Advancing Room-Temperature Magnetic Semiconductors with Organic Radical Charge Transfer Cocrystals. Adv. Mater. 37, 2414719 (2025).
Zhu, Y., Jiang, Q., Zhang, J. & Ma, Y. Recent Progress of Organic Semiconductor Materials in Spintronics. Chem. – Asian J. 18, e202201125 (2023).
Novoa, J. J., Deumal, M. & Jornet-Somoza, J. Calculation of microscopic exchange interactions and modelling of macroscopic magnetic properties in molecule-based magnets. Chem. Soc. Rev. 40, 3182–3212 (2011).
Tamura, M. et al. Bulk ferromagnetism in the β-phase crystal of the p-nitrophenyl nitronyl nitroxide radical. Chem. Phys. Lett. 186, 401–404 (1991).
Jiang, Q. et al. Room-Temperature Ferromagnetism in Perylene Diimide Organic Semiconductor. Adv. Mater. 34, 2108103 (2022).
Xiao, X., Wang, H., Urbankowski, P. & Gogotsi, Y. Topochemical synthesis of 2D materials. Chem. Soc. Rev. 47, 8744–8765 (2018).
Venturini, E. L., Azevedo, L. J., Schirber, J. E., Williams, J. M. & Wang, H. H. ESR study of two phases of di[bis(ethylenedithio)tetrathiafulvalene]triiodide [(BEDT-TTF)2I3]. Phys. Rev. B 32, 2819–2823 (1985).
Sugano, T., Saito, G. & Kinoshita, M. Conduction-electron-spin resonance in organic conductors: α and β phases of di[bis(ethylenedithiolo)tetrathiafulvalene]triiodide [(BEDT-TTF)2I3]. Phys. Rev. B 34, 117–125 (1986).
Jia, Y. et al. Band-like transport in solution-processed perylene diimide dianion films with high hall mobility. Natl. Sci. Rev. 11, nwae087 (2024).
Renner, R. et al. Substituent-dependent absorption and fluorescence properties of perylene bisimide radical anions and dianions. Mater. Horiz. 9, 350–359 (2022).
Jia, Y. et al. Electronic Characteristics of Perylene Diimide Anion Radical and Dianion Films by Quantitative Doping. Chem. Res. Chin. Univ. 39, 187–191 (2023).
Funk, T., Deb, A., George, S. J., Wang, H. & Cramer, S. P. X-ray magnetic circular dichroism—a high energy probe of magnetic properties. Coord. Chem. Rev. 249, 3–30 (2005).
van der Laan, G. & Figueroa, A. I. X-ray magnetic circular dichroism—A versatile tool to study magnetism. Coord. Chem. Rev. 277-278, 95–129 (2014).
Yang, J. et al. Evidence of X-Ray Magnetic Circular Dichroism and Low-Field Microwave Absorption in Room-Temperature Organic Ferromagnetic Semiconductor. Interdiscip. Mater. 4, 576–584 (2025).
Liu, Y. et al. Room-temperature long-range ferromagnetic order in a confined molecular monolayer. Nat. Phys. 20, 281–286 (2024).
Stallinga, P. Electronic Transport in Organic Materials: Comparison of Band Theory with Percolation/(Variable Range) Hopping Theory. Adv. Mater. 23, 3356–3362 (2011).
Abdalla, H., Zuo, G. & Kemerink, M. Range and energetics of charge hopping in organic semiconductors. Phys. Rev. B 96, 241202 (2017).
Sirringhaus, H., Sakanoue, T. & Chang, J.-F. Charge-transport physics of high-mobility molecular semiconductors. Phys. status solidi (b) 249, 1655–1676 (2012).
Yu, H., Sun, J. & Heine, T. Predicting Magnetic Coupling and Spin-Polarization Energy in Triangulene Analogues. J. Chem. Theory Comput. 19, 3486–3497 (2023).
Landauer, R. Irreversibility and Heat Generation in the Computing Process. IBM J. Res. Dev. 5, 183–191 (1961).
Lambson, B., Carlton, D. & Bokor, J. Exploring the Thermodynamic Limits of Computation in Integrated Systems: Magnetic Memory, Nanomagnetic Logic, and the Landauer Limit. Phys. Rev. Lett. 107, 010604 (2011).
Yu, H. & Heine, T. Magnetic Coupling Control in Triangulene Dimers. J. Am. Chem. Soc. 145, 19303–19311 (2023).
He, X. et al. Magnetic Properties of Self-Assemble Naphthalene Diimide Radical Aggregates. Small 20, 2311766 (2024).
Allemand, P. M. et al. On the complexities of short range ferromagnetic exchange in a nitronyl nitroxide. Synth. Met. 43, 3291–3295 (1991).
Nakazawa, Y. et al. Low-temperature magnetic properties of the ferromagnetic organic radical, p-nitrophenyl nitronyl nitroxide. Phys. Rev. B 46, 8906–8914 (1992).
Wang, H., Wan, M. & Jin, T. Synthesis, characterization and magnetic properties of NTDIOO derivatives. Solid State Commun. 84, 487–491 (1992).
Kertesz, M. Pancake Bonding: An Unusual Pi-Stacking Interaction. Chem. – A Eur. J. 25, 400–416 (2019).
He, X. et al. Spin Interactions in Planar Naphthalenediimide Anion Radical Crystal: From Isolated Monomer to π-Aggregates. CCS Chem. 7, 2109–2120 (2025).
Gan, H., Jiang, Q. & Ma, Y. A theoretical study on π-stacking and ferromagnetism of the perylene diimide radical anion dimer and tetramer. Phys. Chem. Chem. Phys. 25, 30005–30013 (2023).
Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys.: Condens. Matter 21, 395502 (2009).
Giannozzi, P. et al. Advanced capabilities for materials modelling with Quantum ESPRESSO. J. Phys.: Condens. Matter 29, 465901 (2017).
Giannozzi, P. et al. Quantum ESPRESSO toward the exascale. J. Chem. Phys. 152, 154105 (2020).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized Gradient Approximation Made Simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).
Prandini, G., Marrazzo, A., Castelli, I. E., Mounet, N. & Marzari, N. Precision and efficiency in solid-state pseudopotential calculations. npj Computational Mater. 4, 72 (2018).
Adamo, C. & Barone, V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys. 110, 6158–6170 (1999).
Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (92463310, 22575091 and 52203221)(Q.J.), National Key Research and Development Program of China (2020YFA0714604)(Y.M.), Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates (2023B1212060003)(Q.J.), Guangdong Provincial Quantum Science Strategic Initiative (GDZX2301002)(Q.J.), Funding by Science and Technology Projects in Guangzhou (2024A04J2529) (Q.J.), Young Talent Support Project of Guangzhou Association for Science and Technology (QT2024-001)(Q.J.), the Fundamental Research Funds of State Key Laboratory of Luminescent Materials and Devices (Skllmd-2023-03, Skllmd-2024-23, Skllmd-2024-18, and Skllmd-2025-09) (Q.J.), the open research fund of Songshan Lake Materials Laboratory (2023SLABFK05) (Q.J.), the Fundamental Research Funds for the Central Universities, SCUT (No. 2024ZYGXZR076) (J.Z.).
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Y.M., Q.J. and J.Z. proposed and supervised the whole research. Y.Z. carried out the preparation and characterization of the films. J.Y., W.C., S.T., X.H. helped on the characterization of the films. H.G. carried out theoretical calculations. Y.Z. wrote the original manuscript. Y.Z., Q.J., L.Y., J.Z., and Y.M. revised of the paper. All authors engaged in discussions on the results and provided comments on the paper.
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Zhu, Y., Jiang, Q., Gan, H. et al. Achieving high-performance room-temperature organic ferromagnetic semiconductor films via topochemical reduction. Nat Commun (2026). https://doi.org/10.1038/s41467-026-71866-2
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DOI: https://doi.org/10.1038/s41467-026-71866-2
