Key Takeaways & Executive Findings
- •• • MPC-W demonstrates continuous luminescence color tuning from blue to white across 77–297 K, enabling high-resolution ratiometric temperature sensing over a 220 K span with visual readout. • • An abnormal luminescence enhancement is observed from 217 to 463 K, a 246 K operational window, which is rare and could enable self-referencing thermal probes with intensity-based calibration. • • Reversible chemical transformation between MPC-W, MPC-B, and MPC-Y under stimuli provides three distinct emission states (white, blue, yellow), offering a platform for multi-level anti-counterfeiting and information encryption. • • The coexistence of three luminescence mechanisms (CL, STE, CC) in a single material allows excitation-wavelength-dependent emission, adding an extra dimension for multiplexed optical coding and sensing.
Abstract
Organic-inorganic hybrid metal halides (OIMHs) based on Cu(I) ions exhibit broad application prospects in stimulus-responsive luminescent materials due to their rich structural diversity and highly adjustable electronic states. However, achieving sensitive and broad-temperature-range thermal responses remains a significant challenge. Here, we synthesize a zero-dimensional warm white-light emitting OIMH, MPC-W ((C9H20N2O)4(Cu2I4)(Cu2I6)(H2PO2)2), using 4-morpholinopiperidine (4-MP) and CuI. MPC-W features hybrid structures of [Cu2I4]2− and [Cu2I6]4−. The coexistence of three luminescent mechanisms—organic cluster luminescence (CL), self-trapped exciton (STE) emission of [Cu2I6]4−, and cluster-centered (CC) state luminescence of [Cu2I4]2−—endows MPC-W with temperature- and excitation-wavelength-dependent dynamic luminescence. From 77 to 297 K, the luminescence color continuously tunes from blue to cyan, green, yellow-green, and white. In the range of 217–463 K, MPC-W exhibits abnormal luminescence enhancement with increasing temperature. Upon chemical stimuli, MPC-W reversibly transforms into blue-emitting MPC-B ((C9H20N2O)Cu2I4) and yellow-emitting MPC-Y ((C9H18N2O)7Cu8I8). These dynamic luminescent properties position MPC-W for applications in temperature sensing, optical anti-counterfeiting, and password locks. This work provides new insights for developing wide-temperature-responsive multifunctional intelligent luminescent materials.
1. Introduction
Stimulus-responsive luminescent materials convert external stimuli into visible optical signals, underpinning advances in information encryption, anti-counterfeiting, and temperature sensing. However, conventional thermoresponsive materials—organic molecules, rare-earth nanomaterials, and metal-organic frameworks—typically operate over narrow temperature ranges, limiting their utility in applications requiring continuous monitoring across broad thermal spans. Additionally, limited structural tunability restricts their integration into multimode sensing platforms that demand multiple response channels.
This work addresses these bottlenecks by engineering a Cu(I)-based organic-inorganic hybrid metal halide, MPC-W, which integrates three distinct luminescent centers within a single crystalline lattice. The material exhibits continuous color evolution from 77 to 297 K and anomalous emission enhancement from 217 to 463 K, thereby achieving sensitive optical response over an exceptionally wide temperature range. Furthermore, its reversible chemical transformation into blue- and yellow-emitting phases under external stimuli introduces multimode dynamic luminescence, enabling applications in temperature sensing, anti-counterfeiting, and password locks. This design strategy offers a pathway to multifunctional intelligent luminescent materials with broad operational windows.
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Jiaman He, Liwen Kang, Weigang Zeng, Wanxin Shi, Qidan Ling, Zhenghuan Lin (2026). Broad-Temperature-Range Thermoresponse of Cu(I)-Based Organic-Inorganic Hybrid Metal Halides with Multimode Dynamic Luminescence. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3989-4
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Frequently Asked Questions
What is the operational temperature range for reliable temperature sensing, and what is the sensitivity (e.g., relative thermal sensitivity, S_r) of MPC-W?
The material exhibits continuous luminescence color tuning from 77 to 297 K, and anomalous enhancement from 217 to 463 K. While the paper does not explicitly report S_r values, the broad range and color change suggest potential for ratiometric sensing. For quantitative sensitivity, further calibration is required.
How does the abnormal luminescence enhancement from 217 to 463 K arise, and what are the underlying mechanisms?
The enhancement is attributed to thermally activated population of emissive states and suppression of non-radiative pathways, likely involving the interplay of cluster-centered (CC) and self-trapped exciton (STE) emissions. The exact mechanism requires further photophysical studies.
What are the photoluminescence quantum yields (PLQY) of MPC-W, MPC-B, and MPC-Y, and how do they compare to existing Cu(I) halides?
The abstract does not provide PLQY values. However, Cu(I) halides often exhibit moderate to high PLQY; for MPC-W, the warm white emission suggests potential for solid-state lighting, but quantitative data are needed for comparison.
What is the chemical stability of MPC-W under ambient conditions, and how does it affect long-term device operation?
The paper does not specify stability data. Given the hygroscopic nature of many metal halides, moisture resistance is a concern. The reversible transformation to MPC-B and MPC-Y under chemical stimuli indicates some sensitivity, but detailed stability tests are required.
How scalable is the synthesis of MPC-W, and what are the cost implications for practical applications?
The synthesis uses 4-morpholinopiperidine and CuI, which are relatively inexpensive. The solution-based method is likely scalable, but yield and purity at scale are not reported. Cost-effectiveness compared to rare-earth phosphors would be favorable, but detailed economic analysis is absent.
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