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Low‐dimensional halide perovskites are highly susceptible to thermal quenching (TQ) due to strong soft lattice nature. Currently, examples of thermally enhanced NIR luminescence in low‐dimensional materials are very scarce to the knowledge. Herein, the active role of vibronic coupling is manifested through thermal tunability of broadband NIR emission in 0D W4+‐activated Cs2ZrCl6, leading to anti‐TQ behavior ranging from 80 to 613 K. Interestingly, the internal quantum efficiency is dramatically boosted from 55.9% to 92.9% in Cs2ZrCl6: W4+, Ce4+ while retaining zero‐TQ luminescence between 303 and 423 K. Transient‐state spectroscopy reveal the distribution of thermally released charge carriers among the vibronically coupled d‐electronic states of W4+ ion is responsible for excellent thermal stability. Density functional theory calculations confirm that weak transient lattice distortion of isolated [WCl6]2– octahedra in the excited state can combat TQ enabled by Franck–Condon vibronic coupling. Utilizing this thermal‐tolerant characteristic, both bandwidth‐ and lifetime‐based thermometers have been developed with low temperature uncertainties below 0.12 K. Moreover, NIR spectroscopy‐type sensor is presented for quantitative HF gas detection with concentration‐ and temperature‐dependent high sensing response and low detection limit. These findings may provide a vital insight into vibronic coupling‐assisted heat‐favorable NIR emissions in low‐dimensional materials for versatile applications. A vibronic coupling‐assisted way is provided for circumventing thermal quenching related to transient lattice distortion in 0D halide perovskites, and this study offers comprehending electron–lattice interactions in low‐dimensional host–W4+ dopant systems for the development of thermally tunable NIR spectroscopy applications, such as HF gas sensing and thermometry.

Lanthanide‐based NIR‐II‐emitting materials (1000–1700 nm) show promise for optoelectronic devices, phototherapy, and bioimaging. However, one major bottleneck to prevent their widespread use lies in low quantum efficiencies, which are significantly constrained by various quenching effects. Here, a highly oriented (222) facet is achieved via facet engineering for Cs2NaErCl6 double perovskites, enabling near‐complete suppression of NIR‐II luminescence quenching. The optimally (222)‐oriented Cs2Ag0.10Na0.90ErCl6 microcrystals emit Er3+ 1540 nm light with unprecedented high quantum efficiencies of 90 ± 6% under 379 nm UV excitation (ultralarge Stokes shift >1000 nm), and a record near‐unity quantum yield of 98.6% is also obtained for (222)‐based Cs2NaYb0.40Er0.60Cl6 microcrystallites under 980 nm excitation. With combined experimental and theoretical studies, the underlying mechanism of facet‐dependent Er3+ 1540 nm emissions is revealed, which can contribute to surface asymmetry‐induced breakdown of parity‐forbidden transition and suppression of undesired non‐radiative processes. Further, the role of surface quenching is reexamined by molecular dynamics based on two facets, highlighting the drastic two‐phonon coupling effect of a hydroxyl group to 4I13/2 level of Er3+. Surface‐functionalized facets will provide new insights for tunable luminescence in double perovskites, and open up a new avenue for developing highly efficient NIR‐II emitters toward broad applications. The preferred (222) facet in Cs2NaErCl6 double perovskite is favorable for Er3+ 1540 nm emission with a record quantum yield of 98.6% under 980 nm excitation, which is useful for surface modification. These findings suggest facet engineering is a new way for realizing highly efficient Er3+‐based NIR‐II emitters toward broad applications.

Low‐dimensional halide perovskites are highly susceptible to thermal quenching (TQ) due to strong soft lattice nature. Currently, examples of thermally enhanced NIR luminescence in low‐dimensional materials are very scarce to the knowledge. Herein, the active role of vibronic coupling is manifested through thermal tunability of broadband NIR emission in 0D W 4+ ‐activated Cs 2 ZrCl 6 , leading to anti‐TQ behavior ranging from 80 to 613 K. Interestingly, the internal quantum efficiency is dramatically boosted from 55.9% to 92.9% in Cs 2 ZrCl 6 : W 4+ , Ce 4+ while retaining zero‐TQ luminescence between 303 and 423 K. Transient‐state spectroscopy reveal the distribution of thermally released charge carriers among the vibronically coupled d ‐electronic states of W 4+ ion is responsible for excellent thermal stability. Density functional theory calculations confirm that weak transient lattice distortion of isolated [WCl 6 ] 2– octahedra in the excited state can combat TQ enabled by Franck–Condon vibronic coupling. Utilizing this thermal‐tolerant characteristic, both bandwidth‐ and lifetime‐based thermometers have been developed with low temperature uncertainties below 0.12 K. Moreover, NIR spectroscopy‐type sensor is presented for quantitative HF gas detection with concentration‐ and temperature‐dependent high sensing response and low detection limit. These findings may provide a vital insight into vibronic coupling‐assisted heat‐favorable NIR emissions in low‐dimensional materials for versatile applications.

Context: Essential oils (EOs) have shown the potential to reversibly overcome the stratum corneum (SC) barrier to enhance the skin permeation of drugs.Objective: The effectiveness of turpentine, Angelica, chuanxiong, Cyperus, cinnamon, and clove oils were investigated for the capacity and mechanism to promote skin penetration of ibuprofen.Materials and methods: Skin permeation studies of ibuprofen across rat abdominal skin with the presence of 3% w/v EOs were carried out; samples were withdrawn from the receptor compartment at 8, 10, 22, 24, 26, 28, 32, 36, and 48 h and analyzed for ibuprofen content by the HPLC method. The mechanisms of penetration enhancement of EOs were further evaluated by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) analysis and determination of the properties of EOs. Moreover, the toxicities of EOs on skin cells were also measured.Results: The enhancement ratio (ER) values of turpentine, Angelica, chuanxiong, Cyperus, cinnamon, clove oils and azone were determined to be 2.23, 1.83, 2.60, 2.49, 2.63 and 1.97, respectively. Revealed by ATR-FTIR analysis, a linear relationship (r = 0.9045) was found between the ER values and the total of the shift of peak position of SC lipids. Furthermore, the results of HaCaT skin cell toxicity evaluation revealed that the natural EOs possessed relatively lower skin irritation potential.Conclusion: Compared with azone, the investigated EOs possess significantly higher penetration enhancement effect and lower skin toxicity. EOs can promote the skin permeation of ibuprofen mainly by disturbing rather than extracting the SC lipids.