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. 2026 Jun 18;65(34):e4311658. doi: 10.1002/anie.4311658

Multi‐Stimuli‐Responsive Mechanoluminescent Manganese Halide Toward External‐Light‐Free Photochemistry

Qiushuang Li 1, Jinxing Geng 2, Chengjie Peng 3, Hailan Wang 4, Feng Wang 1, Xihan Yu 1, Wenya Zhao 5, Guanjun Xiao 1,✉, Han Wang 2,✉, Shunxin Li 1,✉, Qiang Xu 3,✉, Tao Yu 4,✉, Bo Zou 1,✉
PMCID: PMC13480587  PMID: 42313718

ABSTRACT

Solvent‐free mechanochemical photosynthesis offers significant advantages in enhancing reaction efficiency and minimizing environmental impact. However, the inherent opacity of conventional reactors greatly impedes their integration with photochemical pathways within the “dark box.” In this regard, we synthesized a mechanoluminescent (ML) manganese halide (ETP)2MnBr4 (ETP = ethyltriphenylphosphonium) to trigger the sulfonylation reaction, achieving a series of alkenyl and allyl sulfones with 65%–85% yields, all without solvents and external light sources. Piezoresponse force microscope measurements and pressure‐dependent dipole moment analysis indicate that mechanical stress enhances local piezoelectric response and thus leads to the intriguing mechanoluminescence. Furthermore, this ML (ETP)2MnBr4 exhibits multi‐stimuli‐responses with considerable piezochromism of redshift by 174 nm and an abnormal anti‐thermal emission quenching. The increased crystal field strength associated with the decreased Mn–Br bond length leads to the stark piezochromism from green to red under high pressure. This study provides a promising ML manganese halide that enables potential applications in sustainable photochemistry, sensing and anti‐counterfeiting.

Keywords: 0D manganese halide, anti‐counterfeiting, high pressure, mechanoluminescence, photosynthesis

A mechanoluminescent manganese halide, (ETP)2MnBr4, enables solvent‐free mechanochemical photochemistry within a “dark box” reactor, achieving efficient sulfonylation without external light sources. Pressure‐enhanced piezoelectric response induces intense mechanoluminescence, while remarkable piezochromism and anti‐thermal quenching reveal its multifunctional stimuli‐responsive behavior for sustainable photochemistry and sensing applications.

graphic file with name ANIE-65-e4311658-g004.jpg

Abbreviations

0D

Zero‐dimensional

ADXRD

Angle‐dispersive x‐ray diffraction

ATQ

Anti‐thermal emission quenching

ETP

Ethyltriphenylphosphonium

GPa

Gigapascals

ML

Mechanoluminescent

NMR

Nuclear magnetic resonance

PL

Photoluminescence

PLE

PL excitation

T–S

Tanabe–Sugano

XRD

X‐ray diffraction

1. Introduction

Photochemical synthesis enabled high‐energy reaction pathways under mild conditions by exciting molecules to an excited state with photons [1, 2], providing a unique approach for transformations that were difficult to achieve through traditional thermochemistry [3]. However, this technology greatly relied on external light sources penetrating the reaction system and often required a large amount of solvent as the reaction medium, which limited its green application. To reduce or even eliminate solvent usage and enhance environmental sustainability, mechanochemistry has recently emerged as a highly promising approach. By leveraging mechanical force to drive reactions, mechanochemical synthesis enabled efficient utilization of solid substrates for reactions and facilitated processes that were challenging to achieve by traditional batch solution synthesis. Nonetheless, the limited transparency of mechanochemical reaction vessels usually hinders the combination of mechanical and photochemical approaches [4, 5, 6, 7, 8, 9].

Mechanoluminescence refers to the emission of light resulting from the fracture or deformation of a solid under mechanical stimuli, which was first documented by Francis Bacon in scraped sugar crystals [10, 11, 12]. The mechanoluminescent (ML) materials can efficiently convert mechanical energy into an endogenous light source [13, 14, 15], thereby enabling photochemical excitation to be achieved in opaque reactors without an external light source. Consequently, ML materials substantially improved both reaction efficiency and sustainability [16, 17, 18]. Likewise, multimodal stimuli‐responsive ML materials provided enhanced information dimensionality and sophisticated tunability. For instance, the europium tungstate phosphor, which exhibited multicolor chromism in response to force, light, and thermal stimulation, provided an ideal platform for developing higher‐dimensional anti‐counterfeiting labels and multifunctional smart sensors [19, 20]. This stimuli‐responsive luminescence enabled materials to dynamically alter their optical output, opening avenues for intelligent devices like sensors, anti‐counterfeiting tags, optical memories, and human‐machine interfaces [21, 22, 23, 24].

Here, we developed a multimodal stimuli‐responsive ML material with considerable piezochromism and unusual anti‐thermal emission quenching (ATQ) in the synthesized zero‐dimensional (0D) manganese halide (ETP)2MnBr4. The structure consists of isolated [MnBr4]2− tetrahedral units, classifying the material as a 0D metal halide rather than a conventional ABX3 perovskite. By employing ML (ETP)2MnBr4 as a light source within the “dark box,” this mechano‐photoexcitation activated the sulfonylation reaction and produced a series of alkenyl and allyl sulfones with significant synthetic value in 65%–85% yields, all without bulk solvents or an external light source. Combined the variable‐temperature ML spectroscopy, piezoresponse force microscope measurements, high‐pressure synchrotron angle‐dispersive XRD measurements, and the theoretical calculations, it is evidenced that pressure effectively augmented local piezoelectric response, thus leading to enhanced ML performance. Furthermore, the ML material exhibited continuous and reversible luminescence piezochromism from green to red under hydrostatic pressure. The green ML emission enabled spatial location, while the piezochromism allowed for stress quantification. Their synergistic combination facilitated a dual‐parameter sensing capability. Likewise, the ML (ETP)2MnBr4 exhibited an abnormal ATQ, suggesting its potential as a temperature‐responsive luminescent material for optical thermal sensing. This work paves the way for the multi‐stimuli‐responsive ML materials toward future applications of sustainable photochemical synthesis, pressure sensing and force‐optical anti‐counterfeiting.

2. Results and Discussion

The 0D manganese halide (ETP)2MnBr4 single crystals were synthesized by a solvent‐evaporating method (see experimental section). In the crystal structure, each Mn2+ ion was coordinated by four Br− ions, forming a typical tetrahedral geometry with Mn–Br bond distances ranging from 2.474 to 2.501 Å (Figure 1a). It is observed that the (ETP)2MnBr4 single crystals exhibited a bright yellow color under daylight, and a bright green fluorescence under UV light. Note that the prepared (ETP)2MnBr4 showed a green mechanoluminescence upon pressing, scratching or grinding (Figure S2, see the corresponding videos inS1–S3). The PL spectra of (ETP)2MnBr4 showed a green light emission, which was related to the 4T1 ‐6A1 spin‐forbidden transition of tetrahedrally coordinated Mn2+ ions [25]. During the grinding process, compounds (ETP)2MnBr4 exhibited intensive mechanoluminescence in the visible region (Video S1, Supporting information). Similarly, when the crystal was smashed using rods made from metal or glass, ML emission was also observed. As shown in Figure 1b, the ML spectrum matched well with the corresponding PL spectrum with high PLQY of 67.2% (Figure S3), indicating that the emission originated from the same luminescent Mn2+centers. We further tested the ML and PL spectra at room temperature and 77 K, respectively (Figures 1c and S1). Both temperature‐dependent ML spectra and PL spectra exhibited a consistent redshift as the temperature decreased. This further confirmed that the luminous center of ML was associated with the tetrahedrally coordinated Mn2+, rather than from surrounding gas discharge.

FIGURE 1.

FIGURE 1

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(a) Crystal structure of (ETP)2MnBr4 (left panel), crystal colors under daylight, and UV light (right panel). (b) Comparisons of PL and ML spectra at room temperature. (c) Comparisons of ML spectra at 77 and 298 K. (d) Amplitude as a function of tip bias (butterfly loop). (e) Dipole moment of [MnBr4]2− under different pressures of 1 atm, 0.6 and 0.9 GPa. (f) Variation of the total relative charge of each element with pressure (1atm, 0.6, and 0.9 GPa). (g) Hydrogen bond interaction of isolated inorganic [MnBr4]2− tetrahedra with surrounding organic molecules. (h) Schematic illustration of ML mechanism

To examine the possibility of mechanically induced charge separation and local electric‐field formation, piezoresponse force microscopy (PFM) measurements were performed on (ETP)2MnBr4 single crystals. The PFM amplitude signal displayed a characteristic butterfly‐shaped loop under positive and negative DC bias sweeps, while the phase signal exhibited a clear hysteresis loop with phase reversal upon bias switching (Figures 1d and S5). Moreover, the effective piezoelectric coefficient d33 reached 50.95 pC/N, demonstrating that mechanical stress can induce substantial polarization charges in this material. This provided direct experimental support for the formation of transient local electric fields during fracture and suggested the involvement of piezoelectricity in the ML excitation process.

To elucidate the pressure effect on the structure and subsequent luminescent properties, in situ high‐pressure angle‐dispersive x‐ray diffraction (ADXRD) measurements were performed at pressures of 1 atm, 0.6 and 0.9 GPa (Figure S4). Structural analysis revealed that the crystal underwent anisotropic compression without a phase transition. The Mn–Br bond lengths decreased progressively with increasing pressure (Table S1), indicating structural distortion that directly lowered the local symmetry of the luminescent centers. Based on the refined crystal structures, we performed electronic structure calculations by the density functional tight‐binding method to quantify the variation of dipole moments for the molecular units under pressure [26]. The periodic table baseline parameters set and a single Γ point was applied for all the cases [27]. The calculated dipole moments for the Mn‐centered tetrahedra increased monotonically from 0.145 eÅ at 1 atm, to 0.154 eÅ at 0.6 GPa, and 0.167 eÅ at 0.9 GPa (Figure 1e). Concurrently, population analysis of each element under different pressures indicated a significant charge redistribution around the Mn ions with increasing pressure, characterized by a net charge transfer from the Br ligands to the central Mn atom. This charge redistribution was responsible for the observed changes in dipole moment, consequently enhancing the piezoelectric response (Figure 1f).

When an external mechanical force is applied to the (ETP)2MnBr4 crystal, crystal fracture generates fresh fracture surfaces and crack tips. Owing to the piezoelectricity enabled by the non‐centrosymmetric crystal structure, polarization charges accumulate on these newly created surfaces and around crack tips, producing transient local electric fields. These local fields promote the release, migration, and recombination of trapped carriers, and the recombination energy is subsequently transferred to the 4T1 excited state of Mn2+, giving rise to green mechanoluminescence through the 4T1–6A1 transition (Figure 1h). In addition, the applied mechanical force induced structural distortion in the (ETP)2MnBr4 lattice, which reduced the inversion symmetry of the luminescent centers and increased the overall dipole moment. Furthermore, the strong intermolecular hydrogen bonding of (ETP)2MnBr4, would enhance the ML effect by suppressing nonradiative relaxation pathways under a stimulus of mechanical force (Figure 1g) [28, 29, 30].

To explore the multimodal stimuli responses of ML (ETP)2MnBr4, we further investigated the pressure‐ and temperature‐dependent PL properties of (ETP)2MnBr4. As a highly effective tuning parameter, pressure not only reduced interatomic distances but also modified electronic orbitals and bonding structures, thereby regulating the physicochemical properties of the material [31, 32, 33]. It is found that the (ETP)2MnBr4 experienced marked piezochromism from green to red with 174 nm redshift (Figure 2a,b,d,e). The emission peak underwent a consistent linear downward shift at a rate of 18.5 nm/GPa with increasing pressure (Figure 2d). This redshift primarily originated from lattice strain induced by unit cell shrinkage, which enhanced d‐d splitting of Mn2+ ions and consequently reduced the energy gap of the (4T1 ‐6A1) transition. The color gamut diagram depicted the progressive change of CIE chromaticity coordinates from (0.23, 0.67) at 1 atm to (0.65, 0.34) at 10.0 GPa (Figure 2c). Moreover, this ML (ETP)2MnBr4 possessed a superior cycling stability of PL intensity and wavelength against pressure treatments (Figure 2f). The absorption edge and PL spectra of (ETP)2MnBr4 under ambient conditions were shown in Figure 2g, which indicated a large Stokes shift. Using the Tauc plot method, the bandgap value exhibited a linear change at 0.06 eV/GPa with pressure (Figures 2h and S6).

FIGURE 2.

FIGURE 2

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(a) Pressure‐dependent PL photographs of (ETP)2MnBr4. (b) PL spectra of (ETP)2MnBr4 with increasing pressure. (c) Chromaticity coordinates the emissions under pressure. (d) PL peak position evolution with pressure. (e) Pseudo‐color mapping of emission spectra. (f) Cycling stability of PL spectra after ternary pressure treatments from 10 GPa. (g) UV–vis absorption and PL spectra of (ETP)2MnBr4 under ambient conditions. (h) Bandgap evolution of (ETP)2MnBr4 under pressure

In situ high‐pressure Raman spectroscopy and ADXRD patterns of (ETP)2MnBr4 were performed to characterize structural variations. As pressure increased, the Raman peak near 250 cm− 1 experienced a progressive shift toward higher wavenumbers, which indicated the pressure‐induced contraction of the [MnBr4]2− tetrahedra (Figure 3a). In situ high‐pressure ADXRD patterns suggested no phase transition with only the shrinkage of the lattice throughout the compression process (Figure S7,S8 and 3b). Figure 3c presented schematic illustration of the Mn2+‐related emission arising from intra‐atomic transitions within the split d‐orbital energy levels. Upon excitation, electrons underwent transitions from the 6A1 ground state to various excited states of Mn2+, which were categorized into two distinct groups of absorption bands: D‐terms and G‐terms energy levels. The green emission originated from the spin‐forbidden d–d transition of Mn2+ ions. In a tetrahedral coordination environment with weak crystal field strength, Mn2+ promoted a green emission characteristic. As pressure increased, the peak shift in the emission spectra was governed by the crystal field splitting energy (Δ = kRMn‐Br −5), which was primarily determined by the distance R between the central Mn2 + ion and the coordinating Br− ligands. Upon compression, the length of the Mn─Br bonds continuously decreased (Figure 3d), contributing to the enhancement of the crystal field splitting energy [34]. In addition, the minimum distance between Mn atoms (Table S1) excluded the effect of Mn─Mn coupling interaction on the crystal field splitting energy, which typically occurred when the interatomic distance was below 6 Å [35].

FIGURE 3.

FIGURE 3

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(a) Raman spectra of (ETP)2MnBr4 as a function of pressure. (b) Pressure dependence of lattice constants. (c) Schematic illustration of energy levels and optical transitions in tetrahedrally coordinated Mn2+. (d) Mn─Br bond length changes as a function of pressure. (e) T‐S diagram for Mn2+ ion in tetrahedron Td symmetry associated with 1 atm, 4 and 5.3 GPa (f) Hirshfeld surface analysis at 1 atm, 5.3 and 10.0 GPa. (g) Temperature‐dependent emission spectra of (ETP)2MnBr4. (h) Pseudo‐color mapping of emission spectra

Furthermore, the PL excitation (PLE) spectra of (ETP)2MnBr4 was measured under pressure (Figure S9). The Tanabe–Sugano (T–S) diagram in Figure 3e was calculated as a function of crystal‐field splitting energy in Td symmetry using the Racah parameters B and C derived from fitting the experimental excitation wavelength. The various Racah related parameters for the Mn2+ ion within (ETP)2MnBr4 under pressures were depicted in Table S2. The Dq/B increased with increasing pressure, resulting in a significant d–d splitting of Mn2+ and correspondingly reducing the energy difference of the lowest d–d transition (4T1 ‐6A1), thereby resulting in a significant redshift of the emission. The infrared spectrum showed that under compression, the C─H (∼3060 cm−1) and C═C (∼1600 cm−1) stretching vibrations shifted to higher wavenumbers, indicating enhanced intermolecular interactions (Figure S10). The hydrogen bonding interaction between organic molecules (ETP+) and inorganic tetrahedral ([MnBr4]2−) was greatly enhanced under high pressure, which was also responsible for the red shift. We further investigated the temperature response of the ML (ETP)2MnBr4, which was recorded over the range of 100 to 320 K. Notably, the PL emission of (ETP)2MnBr4 exhibited an exceptional ATQ effect (Figure 3g,h). It is unambiguously observed that the PL intensity of (ETP)2MnBr4 gradually increased with increasing temperature from 100 to 320 K. Temperature‐dependent XRD measurements conducted from 153 to 333 K confirm that the crystal structure remains stable throughout this temperature range, with no obvious phase transition observed (Figure S11). Further structural refinement reveals a gradual decrease in the shortest Mn‐Mn distance with increasing temperature (Figure S12). Specifically, the shortened Mn–Mn distance at elevated temperature may enhance orbital overlap and improve Dexter‐type energy transfer efficiency between Mn2+ centers, thereby promoting radiative recombination and giving rise to the ATQ behavior [36, 37].

The as‐synthesized (ETP)2MnBr4 can be fabricated into customized patterns with diverse shapes, as shown in Figure 4a,b. Under ultraviolet or blue excitation, as well as upon just mechanical scratching, these patterns emitted bright green light. This stimuli‐responsive behavior—activatable by either UV light or mechanical stress—demonstrated that the sample was potential for the display and anticounterfeiting with unique patterns or Morse code sequence. Specific information encoded into the material can be retrieved upon exposure to certain external stimuli (e.g., UV light or mechanical force), thus enabling high‐security information encryption. Moreover, we found that the introduction of 0.1 wt.% ML (ETP)2MnBr4 was able to increase significantly the photoluminescence response of the ink HEA‐AA by up to about 25 times, which endows the ML (ETP)2MnBr4 with an additional functionality. (Figures S13 and S14).

FIGURE 4.

FIGURE 4

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(a) Photographs of a rose pattern under different excitations. (b) Imaging patterns of (ETP)2MnBr4 when subjected to scratching. (c) Illustration of mechano‐photoexcitation. (d) Reaction set‐up and substrate scope via mechanochemical sulfonylation reaction. A series of alkenyl sulfones (3a‐3d) and allyl sulfones (4a–4d) were synthesized by using the ML (ETP)2MnBr4 as a light source. The isolated yields of all products are marked below the corresponding structural formulas

We further developed a self‐sustained photochemical synthesis strategy driven exclusively by mechanical stimulation. The ML (ETP)2MnBr4 was used as a light source within the “dark box” reactor to excite the sulfonylation reaction. The ML material proved indispensable, as its omission or replacement with inert additives completely suppressed product formation. This confirms direct photon‐driven activation rather than thermal or mechanical effects (Figure S15 and Table S3). With optimized reaction conditions established, the substrate scope of this mechanochemical sulfonylation reaction was systematically explored. As shown in Figure 4d, a series of alkenyl sulfones 3 and allyl sulfones 4 were formed with yields of 65%–85%. The resulting compounds displayed distinct characteristics in their nuclear magnetic resonance (NMR) spectra (Figure S17–S23). Under the mechanical force generated by high‐speed ball milling, the (ETP)2MnBr4 material was effectively excited, emitting intense green light that promoted the transformation and enabled the successful synthesis of 8 distinct products. This process achieved efficient conversion of mechanical energy into light energy and ultimately into chemical energy. The mechanical excitation of (ETP)2MnBr4 generated photons, which efficiently triggered mechanochemical sulfonylation reaction (Figure S24) [38, 39, 40]. Importantly, this mechanochemical strategy offered significant green chemistry advantages, including solvent‐free operation, reduced waste generation, shorter reaction times, and enhanced space‐time yield [41]. As a result, the limitations associated with external light sources—such as limited penetration depth and energy dissipation—were effectively circumvented, enabling precise photochemical activation under completely solvent‐free conditions. This study established a robust foundation for the development of self‐powered green photochemistry, benefitting from the unique ML manganese halide that operated solely on mechanical energy input, all without solvents and external light sources [42].

3. Conclusion

In summary, we reported a smart 0D manganese halide (ETP)2MnBr4 that exhibited multimodal responses to mechanical force, light and thermal stimuli. By harnessing its green emission induced by mechanical force, we developed a self‐sustained photochemical synthesis strategy driven exclusively by mechanical stimulation. The ML (ETP)2MnBr4 was used to trigger the sulfonylation reaction and produced a series of alkenyl and allyl sulfones with 65%–85% yields, all without bulk solvents or an external light source. PFM measurements and pressure‐dependent dipole analysis indicate that mechanical stress enhances local piezoelectric response and thus leading to the intriguing mechanoluminescence. Moreover, a considerable piezochromism from green to red emission was achieved in the ML (ETP)2MnBr4. The observed redshift was primarily attributed to the enhanced crystal field effects and contraction of the Mn─Br bonds. Furthermore, the PL intensity increased with heating, showing typical ATQ with increasing temperature. This work paves the way for the multi‐stimuli‐responsive ML materials toward future applications of sustainable photochemistry, pressure sensing and force‐optical anti‐counterfeiting.

Conflicts of Interest

The authors declare no conflicts of interest.

Supporting information

Supporting File 1: anie73188‐sup‐0001‐SuppMat.docx.

ANIE-65-e4311658-s002.docx (5.2MB, docx)

Supporting File 2: anie73188‐sup‐0002‐VideoS1.mp4.

Download video file (1.5MB, mp4)

Supporting File 3: anie73188‐sup‐0003‐VideoS2.mp4.

Download video file (627.7KB, mp4)

Supporting File 4: anie73188‐sup‐0004‐VideoS3.mp4.

Download video file (454KB, mp4)

Acknowledgments

This work is supported by the Fundamental and Interdisciplinary Disciplines Breakthrough Plan of the Ministry of Education of China (JYB2025XDXM403), the National Key R&D Program of China (2023YFA1406200), the National Natural Science Foundation of China (T2521005, 12174144, 12474009, 62304089, 12305002 and 124B2059). In situ high‐pressure angle‐dispersive synchrotron XRD measurements were performed at BL15U1 at the Shanghai Synchrotron Radiation Facility (SSRF). The authors thank the staff from SSRF at BL15U1, and User Experiment Assist System.

Contributor Information

Guanjun Xiao, Email: xguanjun@jlu.edu.cn.

Han Wang, Email: hanwang@nwu.edu.cn.

Shunxin Li, Email: shunxin2021@jlu.edu.cn.

Qiang Xu, Email: xuq@jlu.edu.cn.

Tao Yu, Email: iamtyu@nwpu.edu.cn.

Bo Zou, Email: zoubo@jlu.edu.cn.

Data Availability Statement

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

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Associated Data

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Supplementary Materials

Supporting File 1: anie73188‐sup‐0001‐SuppMat.docx.

ANIE-65-e4311658-s002.docx (5.2MB, docx)

Supporting File 2: anie73188‐sup‐0002‐VideoS1.mp4.

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Supporting File 3: anie73188‐sup‐0003‐VideoS2.mp4.

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Supporting File 4: anie73188‐sup‐0004‐VideoS3.mp4.

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Data Availability Statement

The data that support the findings of this study are available on request from the corresponding author. The data are not publicly available due to privacy or ethical restrictions.

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