1.Key Laboratory of Magnetic Molecules and Magnetic Information Material, Ministry of Education, School of Chemistry and Chemistry Engineering, Shanxi Normal University, Taiyuan, China
2.College of Chemistry & Chemical Engineering, College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan, China
3.Department of Applied Chemistry, Yuncheng University, Yuncheng, Shanxi, China
Guojun Zhou (zhougj@sxnu.edu.cn)
Jianwei Qiao (qiaojianwei@tyut.edu.cn)
Xian-Ming Zhang (zhangxianming@tyut.edu.cn)
收稿:2025-09-20,
修回:2025-11-30,
录用:2025-12-01,
网络首发:2026-01-28,
纸质出版:2026-03-31
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Guojun Zhou, Pei Wang, Qiqiong Ren, 等. Spin-canted Mn–Mn coupling in symmetry-broken metal chloride dimer with dual-responsive luminescence and sensing[J]. Light: Science & Applications, 2026,15(3):1007-1016.
Zhou, G. J. et al. Spin-canted Mn–Mn coupling in symmetry-broken metal chloride dimer with dual-responsive luminescence and sensing. Light: Science & Applications, 15, 1007-1016 (2026).
Guojun Zhou, Pei Wang, Qiqiong Ren, 等. Spin-canted Mn–Mn coupling in symmetry-broken metal chloride dimer with dual-responsive luminescence and sensing[J]. Light: Science & Applications, 2026,15(3):1007-1016. DOI: 10.1038/s41377-025-02154-9.
Zhou, G. J. et al. Spin-canted Mn–Mn coupling in symmetry-broken metal chloride dimer with dual-responsive luminescence and sensing. Light: Science & Applications, 15, 1007-1016 (2026). DOI: 10.1038/s41377-025-02154-9.
Magneto-optical coupling provides a powerful alternative to crystal field engineering for modulating Mn
2+
luminescence. However
precise control over Mn–Mn coupling is hindered by the complex spin-electron super-exchange interactions. Herein
we report a symmetry-broken Mn(Ⅱ) chloride dimer
(C
10
H
20
O
5
Mn)(CH
3
CN)MnCl
4
synthesized through a crown-ether-assisted supramolecular strategy. The dimer features a 7-coordinated pentagonal bipyramid and a 4-coordinated tetrahedron linked by a distorted Mn–Cl–Mn bridge (129°)
which promotes rare spin-canted Mn–Mn coupling and creates a novel Mn–Mn luminescent center. This center exhibits a red emission at 638 nm with an unusually short lifetime of 0.42 ms
which is attributed to the relaxation of spin-forbidden
d
–
d
transitions. Notably
the emission undergoes a 30 nm blue-shift upon heating (5–305 K) due to the thermal suppression of spin-canting
and a 40 nm blue-shift under applied pressure (0–20 MPa) resulting from reduced orbital overlap. This dual-responsive luminescence originates from spin-canted weak ferromagnetism
which induces a rearrangement of energy-levels by separating antibonding orbitals. Using this effect
we have demonstrated an optical manometer for real-time underwater depth sensing. These findings highlight spin-canted Mn(Ⅱ) dimers as a promising platform for stimuli-responsive luminescence and reveal a new mechanism for
d
–
d
transition modulation.
He, J. Q. et al. Contactless user-interactive sensing display for human–human and human–machine interactions. Adv. Mater. 36 , 2401931 (2024)..
Liu, K. J. et al. Stimuli-responsive emission from hybrid metal halides. Adv. Funct. Mater. 34 , 2309296 (2024)..
Lou, K. et al. Information storage based on stimuli-responsive fluorescent 3D code materials. Adv. Funct. Mater. 32 , 2113274 (2022)..
Wu, R. et al. Water-triggered stimuli-responsive luminescent crown-ether-coordinated cuprous bromides for multi-functional applications. Chem. Eng. J. 504 , 158913 (2025)..
Liu, D. Y. et al. Multiple stimuli-responsive luminescent chiral hybrid antimony chlorides for anti-counterfeiting and encryption applications. Angew. Chem. Int. Ed. 62 , e202307875 (2023)..
Furasova, A. et al. Structural colouring and luminescence anisotropy of perovskite thin films via laser-induced periodic surface structure formation. Light Adv. Manuf. 6 , 416–427 (2025)..
Zhou, G. J. et al. Temperature/component-dependent luminescence in lead-free hybrid metal halides for temperature sensor and anti-counterfeiting. Adv. Funct. Mater. 34 , 2401860 (2024)..
Zhou, B. et al. Dynamic magneto-optical response and reversible humidity-sensitive luminescence tuned by intermolecular interactions in manganese halides. Adv. Funct. Mater. 35 , 2503326 (2025)..
Mao, L. L. et al. Design principles for enhancing photoluminescence quantum yield in hybrid manganese bromides. J. Am. Chem. Soc. 142 , 13582–13589 (2020)..
Yun, R. et al. Recent advances on Mn 2+ -doping in diverse metal halide perovskites. Laser Photonics Rev. 17 , 2200524 (2023)..
Cong, L. et al. Reversible thermodynamic phase-transition in zero-dimensional manganese halides enables dual-secure optical information anti-counterfeiting and encryption. Laser Photonics Rev. 19 , e00761 (2025)..
Zhou, Q. et al. Mn 2+ and Mn 4+ red phosphors: synthesis, luminescence and applications in WLEDs. A review. J. Mater. Chem. C. 6 , 2652–2671 (2018)..
Qiao, J. W. et al. Compositional engineering of phase-stable and highly efficient deep-red emitting phosphor for advanced plant lighting systems. Light Sci. Appl. 13 , 319 (2024)..
Suo, H. et al. Excitation-mode-selective emission through multiexcitonic states in a double perovskite single crystal. Light Sci. Appl. 14 , 21 (2025)..
Zhou, G. J. et al. Coordination units of Mn 2+ modulation toward tunable emission in zero-dimensional bromides for white light-emitting diodes. J. Mater. Chem. C. 10 , 2095–2102 (2022)..
Su, B. B. et al. Mn 2+ -doped metal halide perovskites: structure, photoluminescence, and application. Laser Photonics Rev. 15 , 2000334 (2021)..
Fu, P. F. et al. Photoluminescence behavior of zero-dimensional manganese halide tetrahedra embedded in conjugated organic matrices. J. Phys. Chem. Lett. 12 , 7394–7399 (2021)..
Yan, S. Y. et al. Synthesis of 0D manganese-based organic–inorganic hybrid perovskite and its application in lead-free red light-emitting diode. Adv. Funct. Mater. 31 , 2100855 (2021)..
Xiao, Y. et al. Tracing the origin of near-infrared emissions emanating from manganese (Ⅱ). Light Sci. Appl. 14 , 194 (2025)..
Zeng, Z. C. et al. Increasing the magnetic transition dipole moment of chiral perovskite through Eu 3+ doping. Adv. Phys. Res. 3 , 2400064 (2024)..
Mai, H. X. et al. Data driven high quantum yield halide perovskite phosphors design and fabrication. Mater. Today 74 , 12–21 (2024)..
Liu, Y. -H. et al. Water-stable 0D hybrid manganese halides with adjustable crystal structure and emission color. Adv. Opt. Mater. 11 , 2301010 (2023)..
Xiao, H. et al. Solvatochromic photoluminescent effects in all-inorganic manganese(Ⅱ)-based perovskites by highly selective solvent-induced crystal-to-crystal phase transformations. Angew. Chem. Int. Ed. 60 , 3699–3707 (2021)..
Chang, T. et al. Temperature-dependent reversible optical properties of Mn-based organic–inorganic hybrid (C 8 H 20 N) 2 MnCl 4 metal halides. ACS Appl. Mater. Interfaces 15 , 5487–5494 (2023)..
Niu, X. Y. et al. The first chiral cerium halide towards circularly-polarized luminescence in the UV region. Sci. China Chem. 67 , 1961–1968 (2024)..
Zhang, K. et al. Effect of Mn–Mn magnetic ordering on photoluminescence in 2D layered hybrid perovskite (CH 3 NH 3 ) 2 MnCl 4 . Adv. Opt. Mater. 12 , 2400936 (2024)..
Chen, H. et al. Antiferromagnetic semiconductor BaFMn 0.5 Te with unique Mn ordering and red photol uminescence. J. Am. Chem. Soc. 141 , 17421–17430 (2019)..
Yang, J. Y., et al. Red-emission harvesting unlocked by pressure-enhanced crystal field and Mn–Mn coupling. Laser Photon. Rev. (in the press).
Higashi, K. et al. Enhanced magnetic interaction by face-shared hydride anions in 6H-BaCrO 2 H. Inorg. Chem. 60 , 11957–11963 (2021)..
Zhu, X. L. et al. Isolated-Mn 2+ -like luminescent behavior in CsMnF 3 caused by competing magnetic interactions at cryogenic temperature. J. Phys. Chem. C. 125 , 27800–27809 (2021)..
Vink, A. P. et al. Luminescence of exchange coupled pairs of transition metal ions. J. Electrochem. Soc. 148 , E313–E320 (2001)..
van Bunningen, A. J., Keizer, S. T. & Meijerink, A. Understanding enormous redshifts in highly concentrated Mn 2+ phosphors. J. Mater. Chem. C. 11 , 8961–8970 (2023)..
Liu, H. Z. et al. Realizing red mechanoluminescence of ZnS: Mn 2+ through ferromagnetic coupling. Adv. Funct. Mater. 34 , 2314422 (2024)..
Lu, M. H. et al. Magnetic coupling interaction-related photoluminescence behaviors in all-inorganic manganese chloride perovskites. Mater. Today Chem. 38 , 102043 (2024)..
Hou, L. P. et al. Spin-exciton interaction and related micro-photoluminescence spectra of ZnSe: Mn DMS nanoribbon. Nanotechnology 28 , 105202 (2017)..
Song, E. H. et al. Tailored near-infrared photoemission in fluoride perovskites through activator aggregation and super-exchange between divalent manganese ions. Adv. Sci. 2 , 1500089 (2015)..
Wang, W. et al. Mn–Mn magnetic coupling interaction-induced red emission in a tetra-coordinated lattice. Chem. Mater. 36 , 5574–5586 (2024)..
Zhu, X. L. et al. Suppressing energy migration via antiparallel spin alignment in one-dimensional Mn 2+ halide magnets with high luminescence efficiency. Angew. Chem. Int. Ed. 64 , e202417218 (2025)..
Liu, Y. et al. New insights into Mn–Mn coupling interaction-directed photoluminescence quenching mechanism in Mn 2+ -doped semiconductors. J. Am. Chem. Soc. 142 , 6649–6660 (2020)..
Bonnin, M. A. & Feldmann, C. Insights of the structure and luminescence of Mn 2+ /Sn 2+ -containing crown-ether coordination compounds. Inorg. Chem. 60 , 14645–14654 (2021)..
Song, E. H. et al. Mn 2+ -activated dual-wavelength emitting materials toward wearable optical fibre temperature sensor. Nat. Commun. 13 , 2166 (2022)..
Luo, C. et al. Quantitative decoupling of strong Mn-Mn coupling on photoluminescence of zero-dimensional hybrid manganese chlorides single crystals. Adv. Opt. Mater. 12 , 2401591 (2024)..
Weng, D. -F., Wang, Z. -M. & Gao, S. Framework-structured weak ferromagnets. Chem. Soc. Rev. 40 , 3157–3181 (2011)..
Dzyaloshinsky, I. A thermodynamic theory of "weak" ferromagnetism of antiferromagnetics. J. Phys. Chem. Solids 4 , 241–255 (1958)..
Moriya, T. Anisotropic superexchange interaction and weak ferromagnetism. Phys. Rev. 120 , 91–98 (1960)..
Ma, X. S. et al. Effect of Dzialoshinski-Moriya interaction on thermal entanglement of a mixed-spin chain. Sci. China Ser. G Phys. Mech. Astron. 51 , 1897–1904 (2008)..
Robinson, K., Gibbs, G. V. & Ribbe, P. H. Quadratic elongation: a quantitative measure of distortion in coordination polyhedra. Science 172 , 567–570 (1971)..
Wei, J. -H. et al. Indium-antimony-halide single crystals for high-efficiency white-light emission and anti-counterfeiting. Sci. Adv. 7 , eabg3989 (2021)..
Mugiraneza, S. & Hallas, A. M. Tutorial: a beginner's guide to interpreting magnetic susceptibility data with the Curie-Weiss law. Commun. Phys. 5 , 95 (2022)..
Liu, S. Q. et al. Intervalence charge transfer of Cr 3+ –Cr 3+ aggregation for NIR-Ⅱ luminescence. Light Sci. Appl. 12 , 181 (2023)..
Wang, X. C. et al. The effect of solvent on the formation of low-dimensional metal halides and their self-trapped exciton emission. Chem. Eng. J. 486 , 150257 (2024)..
Yun, X. Y. et al. Zero-dimensional tellurium-based organic–inorganic hybrid halide single crystal with yellow-orange emission from self-trapped excitons. Nanomaterials 14 , 46 (2024)..
Barthou, C. et al. Mn 2+ concentration effect on the optical properties of Zn 2 SiO 4 : Mn phosphors. J. Electrochem. Soc. 141 , 524–528 (1994)..
Ronda, C. R. & Amrein, T. Evidence for exchange-induced luminescence in Zn 2 SiO 4 : Mn. J. Lumin. 69 , 245–248 (1996)..
Zhu, C. et al. Supramolecular assembly of blue and green halide perovskites with near-unity photoluminescence. Science 383 , 86–93 (2024)..
Ren, Q. Q. et al. Optical activity levels of metal centers controlling multi-mode emissions in low-dimensional hybrid metal halides for anti-counterfeiting and information encryption. Chem. Sci. 15 , 16536–16545 (2024)..
Kennedy, T. A. et al. Symmetry and electronic structure of the Mn impurity in ZnS nanocrystals. Phys. Rev. B 52 , R14356–R14359 (1995)..
Gonzalez Beermann, P. A. et al. EPR spectra of Mn 2+ -doped ZnS quantum dots. Chem. Mater. 16 , 915–918 (2004)..
Liu, N. -S., Wang, C. & Ji, W. Recent research advances in two-dimensional magnetic materials. Acta Phys. Sin. 71 , 127504 (2022)..
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54 , 11169–11186 (1996)..
Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6 , 15–50 (1996)..
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77 , 3865–3868 (1996)..
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