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1.
Anal Chem ; 96(23): 9399-9407, 2024 Jun 11.
Article in English | MEDLINE | ID: mdl-38804597

ABSTRACT

Fast and efficient sample pretreatment is the prerequisite for realizing surface-enhanced Raman spectroscopy (SERS) detection of trace targets in complex matrices, which is still a big issue for the practical application of SERS. Recently, we have proposed a highly performed liquid-liquid extraction (LLE)-back extraction (BE) for weak acids/bases extraction in drinking water and beverage samples. However, the performance efficiency decreased drastically on facing matrices like food and biological blood. Based on the total interaction energies among target, interferent, and extractant molecules, solid-phase extraction (SPE) with a higher selectivity was introduced in advance of LLE-BE, which enabled the sensitive (µg L-1 level) and rapid (within 10 min) SERS detection of both koumine (a weak base) and celastrol (a weak acid) in different food and biological samples. Further, the high SERS sensitivity was determined unmanned by Vis-CAD (a machine learning algorithm), instead of the highly demanded expert recognition. The generality of SPE-LLE-BE for various weak acids/bases (2 < pKa < 12), accompanied by the high efficiency, easy operation, and low cost, offers SERS as a powerful on-site and efficient inspection tool in food safety and forensics.


Subject(s)
Solid Phase Extraction , Spectrum Analysis, Raman , Spectrum Analysis, Raman/methods , Liquid-Liquid Extraction , Humans , Pentacyclic Triterpenes , Food Analysis/methods , Metal Nanoparticles/chemistry
2.
Inorg Chem ; 63(9): 4288-4298, 2024 Mar 04.
Article in English | MEDLINE | ID: mdl-38369784

ABSTRACT

Ba3Lu(BO3)3(BLB):Ce3+,Tb3+/Mn2+ phosphors were designed to explore effective and multifunctional applications. Under the excitation of near-ultraviolet (n-UV) light, the BLB:Ce3+ phosphor showed broad-band blue emission. After codoping with Mn2+ ions, the single-phase white light phosphor is achieved through the energy transfer (ET) between Ce3+ and Mn2+. In addition, thermal stability is significantly enhanced by the addition of Tb3+ (BLB:0.02Ce3+,0.20Tb3+) compared to that codoped with Mn2+ (BLB:0.02Ce3+,0.10Mn2+). The light-emitting diode (LED) device with warm white light emission is fabricated with UV-chip-coated BLB:0.02Ce3+,0.05Tb3+ and Sr2Si5N8:Eu2+ phosphors, showing a good potential application value for LEDs. Additionally, the spectral properties of borate-based phosphors (BLB:0.02Ce3+) under high pressure were studied for the first time. Surprisingly, the change of pressure enabled the emission peak of BLB:0.02Ce3+ to be tuned from 485 to 552 nm, and dλ/dP is 3.51 nm GPa-1. The color changes from blue to yellow with an increase of pressure. Compared with the reported data, the pressure-sensing sensitivity based on the central peak shift in this work is the highest in all Ce3+ single-doped samples. In addition, the emitting color and intensity were gradually regained after decompression. The intensity can reach 80% of the initial intensity. All data demonstrate that the BLB:0.02Ce3+ phosphor has the potential to be utilized as an optical pressure sensor due to the high-pressure sensitivity and visible color tuning.

3.
Inorg Chem ; 63(11): 5175-5184, 2024 Mar 18.
Article in English | MEDLINE | ID: mdl-38427020

ABSTRACT

Nowadays, the utilization of noncontact temperature and pressure sensing is experiencing growing popularity. In this work, Bi3+, Eu3+-doped Ca5(BO3)3F (CBOF) phosphors were synthesized via an ionic liquid-assisted electrospinning approach. The effect of molecular weight of polyvinylpyrrolidone on the morphology of CBOF was investigated, and a comprehensive analysis of its formation mechanism was presented. The luminescence properties of CBOF: Bi3+, Eu3+ were studied systematically. The temperature-dependent emission of CBOF: Bi3+, Eu3+ phosphor was discussed, and it displayed thermal sensitivity, which can be attributed to the distinct thermal response emission behaviors of Bi3+ and Eu3+. The investigation of the pressure-dependent emission behavior of the CBOF: Bi3+ phosphor revealed an anomalous phenomenon: with the increase of pressure, the emission peak showed a trend of first a blue shift and then a red shift. This anomaly was discussed in detail. The phosphor exhibits visual color change (blue to cyan), remarkable pressure sensitivity (4.76 nm/GPa), and a high upper pressure limit (24.2 GPa), indicating its potential use as an optical pressure sensor. Consequently, this study presents an innovative synthetic approach for fabricating CBOF, presenting a bifunctional material with promising prospects in the fields of temperature and pressure sensing.

4.
Inorg Chem ; 63(24): 11431-11437, 2024 Jun 17.
Article in English | MEDLINE | ID: mdl-38814822

ABSTRACT

Lead-free organic-inorganic hybrid perovskites are one class of promising optoelectronic materials that have attracted much attention due to their outstanding stability and environmentally friendly nature. However, the intrinsic band gap far from the Shockley-Queisser limit and the inferior electrical properties largely limit their applicability. Here, a considerable band-gap narrowing from 2.43 to 1.64 eV with the compression rate up to 32.5% is achieved via high-pressure engineering in the lead-free hybrid perovskite MA3Sb2I9. Meanwhile, the electric transport process changes from the initial interaction of both ions and electrons to only the contribution of electrons upon compression. The alteration in electrical characteristics is ascribed to the vibration limitation of organic ions and the enhanced orbital overlap, resulting from the reduction of the Sb-I bond length through pressure-induced phase transitions. This work not only systematically investigates the correlation between the structural and optoelectronic properties of MA3Sb2I9 but also provides a potential pathway for optimizing electrical properties in lead-free hybrid perovskites.

5.
Nano Lett ; 23(24): 11982-11988, 2023 Dec 27.
Article in English | MEDLINE | ID: mdl-38051759

ABSTRACT

The strained interface of core@shell nanocrystals (NCs) can effectively modulate the energy level alignment, thereby significantly affecting the optical properties. Herein, the unique photoluminescence (PL) response of doped Mn ions is introduced as a robust probe to detect the targeted pressure-strain relation of CdS@ZnS NCs. Results show that the core experiences actually less pressure than the applied external pressure, attributed to the pressure-induced optimized interface that reduces the compressive strain on core. The pressure difference between core and shell increases the conduction band and valence band offsets and further achieves the core@shell configuration transition from quasi type II to type I. Accordingly, the PL intensity of CdS@ZnS NCs slightly increases, along with a faster blue-shift rate of PL peak under low pressure. This study elucidates the interplay between external physical pressure and interfacial chemical stress for core@shell NCs, leading to precise construction of interface engineering for practical applications.

6.
Angew Chem Int Ed Engl ; : e202406015, 2024 Apr 18.
Article in English | MEDLINE | ID: mdl-38635006

ABSTRACT

Piezochromic materials refer to a class of matters that alter their photoluminescence (PL) colors in response to the external stimuli, which exhibit promising smart applications in anti-counterfeiting, optoelectronic memory and pressure-sensing. However, so far, most reported piezochromic materials have been confined to organic materials or hybrid materials containing organic moieties with limited piezochromic range of less than 100 nm in visible region. Here, we achieved an intriguing piezochromism in all-inorganic zero-dimensional (0D) Cs3Cu2Cl5 nanocrystals (NCs) with a considerable piezochromic range of 232 nm because of their unique inorganic rigid structure. The PL energy shifted from the lowest-energy red fluorescence (1.85 eV) to the highest-energy blue fluorescence (2.83 eV), covering almost the entire visible wavelength range. Pressure-modulated self-trapped exciton emission between different energy levels of self-trapped states within Cs3Cu2Cl5 NCs was the main reason for this piezochromism property. Note that the quenched emission, which is over five times more intense than that in the initial state, is retained under ambient conditions upon decompression. This work provides a promising pressure indicating material, particularly used in pressure stability monitoring for equipment working at extreme environments.

7.
Angew Chem Int Ed Engl ; : e202409099, 2024 Jun 24.
Article in English | MEDLINE | ID: mdl-38924238

ABSTRACT

Achieving enhanced or blue-shifted emission from piezochromic materials remains a major challenge. Covalent organic frameworks (COFs) are promising candidates for the development of piezochromic materials owing to their dynamic structures and adjustable optical properties, where the emission behaviors are not solely determined by the functional groups, but are also greatly influenced by the specific geometric arrangement. Nevertheless, this area remains relatively understudied. In this study, a successful synthesis of a series of bicarbazole-based COFs with varying topologies, dimensions, and linkages was conducted, followed by an investigation of their structural and emission properties under hydrostatic pressure generated by a diamond anvil cell. Consequently, these COFs exhibited distinct piezochromic behaviors, particularly a remarkable pressure-induced emission enhancement (PIEE) phenomenon with a 16-fold increase in fluorescence intensity from three-dimensional COFs, surpassing the performance of CPMs and most organic small molecules with PIEE behavior. On the contrary, three two-dimensional COFs with flexible structures exhibited rare blue-shifted emission, whereas the variants with rigid and conjugated structures showed common red-shifted and reduced emission. Mechanism research further revealed that these different piezochromic behaviors were primarily determined by interlayer distance and interaction.

8.
Angew Chem Int Ed Engl ; 63(12): e202319815, 2024 Mar 18.
Article in English | MEDLINE | ID: mdl-38299255

ABSTRACT

Piezochromic materials that exhibit pressure-dependent luminescence variations are attracting interest with wide potential applications in mechanical sensors, anticounterfeiting and storage devices. Crystalline porous materials (CPMs) have been widely studied in piezochromism for highly tunable luminescence. Nevertheless, reversible and high-contrast emission response with a wide pressure range is still challenging. Herein, the first example of hierarchical porous cage-based πOF (Cage-πOF-1) with spring structure was synthesized by using aromatic chiral cages as building blocks. Its elastic properties evaluated based on the bulk modulus (9.5 GPa) is softer than most reported CPMs and the collapse point (20.0 GPa) significantly exceeds ever reported CPMs. As smart materials, Cage-πOF-1 displays linear pressure-dependent emission and achieves a high-contrast emission difference up to 154 nm. Pressure-responsive limit is up to 16 GPa, outperforming the CPMs reported so far. Dedicated experiments and density functional theory (DFT) calculations illustrate that π-π interactions-dominated controllable structural shrinkage and porous-spring-structure-mediated elasticity is responsible for the outstanding piezofluorochromism.

9.
Angew Chem Int Ed Engl ; 63(22): e202403646, 2024 May 27.
Article in English | MEDLINE | ID: mdl-38494740

ABSTRACT

Organic piezochromic materials that manifest pressure-stimuli-responses are important in various fields such as data storage and anticounterfeiting. The manipulation of piezofluorochromic behaviors for these materials is promising but remains a great challenge. Herein, a non-luminous components regulated strategy is developed and organic molecular cages (OMCs), a burgeoning class of crystalline organic materials with structural dynamics, are first explored for the design of piezofluorochromic materials with tunable luminescence. A series of OMCs based on aggregation-induced emission (AIE) chromophores, termed Cage 1-3, are synthesized and their piezofluorochromic behaviors are investigated by diamond anvil cell technique. Due to the sufficient voids between its flexible chromophores offered by the OMC structure, Cage 1 exhibits thermofluorochromic and piezofluorochromic properties. Moreover, the piezofluorochromic performance of this OMC could be further promoted by replacing its non-luminous components with improved flexibilities, and a remarkable luminescence peak shift by 150 nm together with a response sensitivity of 13.8 nm GPa-1 was achieved upon hydrostatic compression. The cage structure plays a vital role in facilitating efficient and reversible piezofluorochromic behaviors. This study has shed light on the rational design and exploitation of OMCs as an exceptional platform to accomplish customizable piezofluorochromic behaviors and enlarge their potential applications in pressure-based luminescence.

10.
Small ; 19(21): e2300455, 2023 May.
Article in English | MEDLINE | ID: mdl-36808884

ABSTRACT

Copper(I)-based halides have recently attracted increasing attention as a substitute for lead halides, owing to their nontoxicity, abundance, unique structure, and optoelectric properties. However, exploring an effective strategy to further improve their optical activities and revealing structure-optical property relationships still remain a great concern. Here, by using high pressure technique, a remarkable enhancement of self-trapped exciton (STE) emission associated with the energy exchange between multiple self-trapped states in zero-dimensional lead-free halide Cs3 Cu2 I5 NCs is successfully achieved. Furthermore, high-pressure processing endows the piezochromism of Cs3 Cu2 I5 NCs by experiencing a white light and a strong purple light emission, which is able to be stabilized at near-ambient pressure. The distortion of [Cu2 I5 ] clusters composing of tetrahedral [CuI4 ] and trigonal planar [CuI3 ] and the decreased Cu-Cu distance between the adjacent Cu-I tetrahedron and triangle are responsible for the significant STEs emission enhancement under high pressure. The experiments combined with first-principles calculations not only shed light on the structure-optical property relationships of [Cu2 I5 ] clusters halide, but also provide guidance for improving emission intensity that is highly desirable in solid-state lighting applications.

11.
Small ; 19(19): e2206932, 2023 May.
Article in English | MEDLINE | ID: mdl-36807515

ABSTRACT

Optical anisotropy, which is quantified by birefringence (Δn) and linear dichroism (Δk), can significantly modulate the angle-resolved polarized Raman spectroscopy (ARPRS) response of anisotropic layered materials (ALMs) by external interference. This work studies the separate modulation of birefringence on the ARPRS response and the intrinsic response by selecting transparent birefringent crystal α-MoO3 as an excellent platform. It is found that there are several anomalous ARPRS responses in α-MoO3 that cannot be reproduced by the real Raman tensor widely used in non-absorbing materials; however, they can be well explained by considering the birefringence-induced Raman selection rules. Moreover, the systematic thickness-dependent study indicates that birefringence modulates the ARPRS response to render an interference pattern; however, the amplitude of modulation is considerably lower than that by linear dichroism as occurred in black phosphorous. This weak modulation brings convenience to the crystal orientation determination of transparent ALMs. Combining the atomic vibrational pattern and bond polarizability model, the intrinsic ARPRS response of α-MoO3 is analyzed, giving the physical origins of the Raman anisotropy. This study employs α-MoO3 as an example, although it is generally applicable to all transparent birefringent ALMs.

12.
Phys Rev Lett ; 130(26): 266001, 2023 Jun 30.
Article in English | MEDLINE | ID: mdl-37450815

ABSTRACT

The search for high-temperature superconducting superhydrides has recently moved into a new phase by going beyond extensively probed binary compounds and focusing on ternary ones with vastly expanded material types and configurations for property optimization. Theoretical and experimental works have revealed promising ternary compounds that superconduct at or above room temperature, but it remains a pressing challenge to synthesize stoichiometric ternary compounds with a well-resolved crystal structure that can host high-temperature superconductivity at submegabar pressures. Here, we report on the successful synthesis of ternary LaBeH_{8} obtained via compression in a diamond anvil cell under 110-130 GPa. X-ray diffraction unveils a rocksalt-like structure composing La and BeH_{8} units in the lattice. Transport measurements determined superconductivity with critical temperature T_{c} up to 110 K at 80 GPa, as evidenced by a sharp drop of resistivity to zero and a characteristic shift of T_{c} driven by a magnetic field. Our experiment establishes the first superconductive ternary compound with a resolved crystal structure. These findings raise the prospects of rational development of the class of high-T_{c} superhydrides among ternary compounds, opening greatly expanded and more diverse structural space for exploration and discovery of superhydrides with enhanced high-T_{c} superconductivity.


Subject(s)
Diamond , Superconductivity , Temperature , Magnetic Fields , Pressure
13.
Crit Rev Food Sci Nutr ; : 1-24, 2023 Jul 15.
Article in English | MEDLINE | ID: mdl-37452658

ABSTRACT

Meat quality holds significant importance for both consumers and meat producers. Various factors influence meat quality, and among them, mitochondria play a crucial role. Recent studies have indicated that mitochondria can sustain their functions and viability for a certain duration in postmortem muscles. Consequently, mitochondria have an impact on oxygen consumption, energy metabolism, and apoptotic processes, which in turn affect myoglobin levels, oxidative stress, meat tenderness, fat oxidation, and protein oxidation. Ultimately, these factors influence the color, tenderness, and flavor of meat. However, there is a dearth of comprehensive summaries addressing the effects of mitochondria on postmortem muscle physiology and meat quality. Therefore, this review aims to describe the characteristics of muscle mitochondria and their potential influence on muscle. Additionally, a suitable method for isolating mitochondria is presented. Lastly, the review emphasizes the regulation of oxygen consumption, energy metabolism, and apoptosis by postmortem muscle mitochondria, and provides an overview of relevant research and recent advancements. The ultimate objective of this review is to elucidate the underlying mechanisms through which mitochondria impact meat quality.

14.
Inorg Chem ; 62(10): 4361-4372, 2023 Mar 13.
Article in English | MEDLINE | ID: mdl-36861488

ABSTRACT

A novel green-light-emitting silicon-based oxynitride phosphor Ca4Y3Si7O15N5:Eu2+ with low thermal quenching and ideal pressure sensitivity is reported. The Ca3.99Y3Si7O15N5:0.01Eu2+ phosphor can be efficiently excited by 345 nm ultraviolet light and shows very low thermal quenching (integrated and peak emission intensities at 373 and 423 K were 96.17, 95.86, and 92.73, 90.66% of those at 298 K, respectively). The correlation between high thermal stability and structural rigidity is investigated in detail. The white-light-emitting diode (W-LED) is assembled by depositing the obtained green-light-emitting phosphor Ca3.99Y3Si7O15N5:0.01Eu2+ and commercial phosphors on a ultraviolet (UV)-emitting chip (λ = 365 nm). The CIE color coordinates, color rendering index (Ra), and corrected color temperature (CCT) of the obtained W-LED are (0.3724, 0.4156), 92.9, and 4806 K, respectively. In addition, when subjected to in situ high-pressure fluorescence spectroscopy, the phosphor exhibits an evident red shift of 40 nm with an increase in pressure from 0.2 to 32.1 GPa. The phosphor has the advantage of high-pressure sensitivity (dλ/dP = 1.13 nm GPa-1) and visualization with pressure changes. The possible reasons and mechanisms are deeply discussed in detail. Based on the above advantages, Ca3.99Y3Si7O15N5:0.01Eu2+ phosphor is expected to have potential applications in W-LEDs and optical pressure sensing.

15.
Sensors (Basel) ; 23(5)2023 Feb 25.
Article in English | MEDLINE | ID: mdl-36904781

ABSTRACT

The cooperative imaging of the bistatic radar is an important research topic for missile-borne radar detection. The existing missile-borne radar detection system is mainly based on the target plot information separately extracted by each radar for data level fusion, without considering the gain brought by the cooperative processing of the radar target echo signal. In this paper, a random frequency-hopping waveform is designed for the bistatic radar to achieve efficient motion compensation. A coherent processing algorithm for bistatic echo signals is designed to achieve band fusion and improve the signal quality and range resolution of the radar. Simulation and high-frequency electromagnetic calculation data were used to verify the effectiveness of the proposed method.

16.
Zhongguo Zhong Yao Za Zhi ; 48(15): 4147-4155, 2023 Aug.
Article in Zh | MEDLINE | ID: mdl-37802783

ABSTRACT

Based on the androgen receptor(AR)/mammalian target of rapamycin(mTOR)signaling pathway, the effects of Xihuang Pills-medicated serum on the proliferation and apoptosis of prostate cancer LNCaP cells were investigated. The drug-containing serum of SD rats was prepared by intragastric administration of Xihuang Pills suspension. The effects of low-, medium-, and high-dose Xihuang Pills-containing serum on the in vitro proliferation of LNCaP cells were detected by cell counting kit-8(CCK-8). Flow cytometry was used to detect the apoptosis level of LNCaP cells after intervention with different concentrations of Xihuang Pills. Protein expression of cleaved cysteinyl aspartate-specific proteinase caspase-3(cleaved caspase-3), B-cell lymphoma-2(Bcl-2), and AR as well as the phosphorylation level of mTOR protein were detected by Western blot. The results showed that compared with the blank serum, the drug-medicated serum could blunt the activity of LNCaP cells. Low-, medium-, and high-dose Xihuang Pills-containing serum could significantly increase the cell apoptosis rate, increase the expression of cleaved caspase-3 protein, decrease the expression of Bcl-2 protein, reduce the expression of AR protein, and down-regulate the level of phosphorylated mTOR(p-mTOR). To study the effect of Xihuang Pills on the growth of LNCaP cells in vivo, different doses of Xihuang Pills were used to intervene in the subcutaneous graft model in nude mice inoculated with LNCaP cells. The expression levels of AR, mTOR, p-mTOR, Bcl-2, and cleaved caspase-3 were detected by Western blot. The results showed that the volumes of subcutaneous graft tumor in the low-dose, medium-dose, and high-dose Xihuang Pills groups significantly decreased compared with that in the model group. The weight of subcutaneous transplanted tumor in each group with drug intervention was significantly lower than that in the model group. Compared with the model group, the low-dose, medium-dose, and high-dose Xihuang Pills groups showed increased cleaved caspase-3 protein expression, decreased Bcl-2 and AR protein expression, and reduced p-mTOR protein expression. Further experiments showed that AR agonist R1881 could block the anti-proliferation and pro-apoptotic effects of Xihuang Pills. The mechanism of Xihuang Pills against prostate cancer is related to the inhibition of the AR/mTOR signaling pathway, inhibition of LNCaP cell proliferation, and induction of apoptosis in cancer cells.


Subject(s)
Prostatic Neoplasms , Signal Transduction , Humans , Male , Mice , Rats , Animals , Caspase 3/genetics , Caspase 3/metabolism , Mice, Nude , Cell Line, Tumor , Rats, Sprague-Dawley , TOR Serine-Threonine Kinases/genetics , TOR Serine-Threonine Kinases/metabolism , Prostatic Neoplasms/drug therapy , Prostatic Neoplasms/pathology , Cell Proliferation , Apoptosis , Proto-Oncogene Proteins c-bcl-2/metabolism , Mammals/metabolism
17.
Angew Chem Int Ed Engl ; 62(39): e202308662, 2023 Sep 25.
Article in English | MEDLINE | ID: mdl-37565546

ABSTRACT

Optical force probes that can release force-dependent and visualized signals with minimal changes in the polymer main chains under mechanical load are highly sought after but currently limited. In this study, we introduce a flex-activated mechanophore (FA) based on the Diels-Alder adduct of anthracene and dimethyl acetylenedicarboxylatea that exhibits turn-on mechanofluorescence. We demonstrate that when FA is incorporated into polymer networks or in its crystalline state, it can release fluorescent anthracenes through a retro-Diels-Alder mechanochemical reaction under compression or hydrostatic high pressure, respectively. The flex-activated mechanism of FA is successfully confirmed. Furthermore, we systematically modulate the force delivered to the mechanophore by varying the crosslinking density of the networks and the applied macroscopic pressures. This modulation leads to incremental increases in mechanophore activation, successive release of anthracenes, and quantitative enhancement of fluorescence intensity. The exceptional potential of FA as a sensitive force probe in different bulk states is highlighted, benefiting from its unique flex-activated mode with highly emissive fluorophore releasing. Overall, this report enriches our understanding of the structures and functions of flex-activated mechanophores and polymeric materials.

18.
Angew Chem Int Ed Engl ; 62(46): e202311912, 2023 Nov 13.
Article in English | MEDLINE | ID: mdl-37794619

ABSTRACT

The excellent luminescence properties and structural dynamics driven by the stereoactivity of the lone pair in a variety of low-dimensional ns2 metal halides have attracted growing investigations for optoelectronic applications. However, the structural and photophysical aspects of the excited state associated with the lone pair expression are currently open questions. Herein, zero-dimensional Sn-based halides with static stereoactive 5 s2 lone pairs are selected as a model system to understand the correlations between the distinctive lone pair expression and the excited-state structural relaxation and charge carrier dynamics by continuous lattice manipulation. Lattice compression drives 5 s2 lone pair active switching and self-trapped exciton (STE) redistribution by suppressing excited-state structural deformation of the isolated SnBr4 2- units. Our results demonstrate that the static expression of the 5 s2 lone pair results in a red broadband triplet STE emission with a large Stokes shift, while its dynamic expression creates a sky-blue narrowband emission dominated by the radiative recombination of singlet STEs. Our findings and the photophysical mechanism proposed highlight the stereochemical effects of lone pair expression in controlling light emission properties and offer constructive guidelines for tuning the optoelectronic properties in diverse ns2 metal halides.

19.
Angew Chem Int Ed Engl ; 62(14): e202301573, 2023 Mar 27.
Article in English | MEDLINE | ID: mdl-36738102

ABSTRACT

Pressure-induced emission (PIE) associated with self-trapping excitons (STEs) in low-dimensional halide perovskites has attracted great attention for better materials-by-design. Here, using 2D layered double perovskite (C6 H5 CH2 CH2 NH3 + )4 AgBiBr8 as a model system, we advance a fundamental physicochemical mechanism of the PIE from the perspective of carrier dynamics and excited-state behaviors of local lattice distortion. We observed a pressure-driven STE transformation from dark to bright states, corresponding a strong broadband Stokes-shifted emission. Further theoretical analysis demonstrated that the suppressed lattice distortion and enhanced electronic dimensionality in the excited-state play an important role in the formation of stabilized bright STEs, which could manipulate the self-trapping energy and lattice deformation energy to form an energy barrier between the potential energy curves of ground- and excited-state, and enhance the electron-hole orbital overlap, respectively.

20.
Angew Chem Int Ed Engl ; 62(27): e202304234, 2023 Jul 03.
Article in English | MEDLINE | ID: mdl-37134296

ABSTRACT

Piezochromic materials with pressure-dependent photoluminescence tuning properties are important in many fields, such as mechanical sensors, security papers, and storage devices. Covalent organic frameworks (COFs), as an emerging class of crystalline porous materials (CPMs) with structural dynamics and tunable photophysical properties, are suitable for designing piezochromic materials, but there are few related studies. Herein, we report two dynamic three-dimensional COFs based on aggregation-induced emission (AIE) or aggregation-caused quenching (ACQ) chromophores, termed JUC-635 and JUC-636 (JUC=Jilin University China), and for the first time, study their piezochromic behavior by diamond anvil cell technique. Due to the various luminescent groups, JUC-635 has completely different solvatochromism and molecular aggregation behavior in the solvents. More importantly, JUC-635 with AIE effect exhibits a sustained fluorescence upon pressure increase (≈3 GPa), and reversible sensitivity with high-contrast emission differences (Δλem =187 nm) up to 12 GPa, superior to other CPMs reported so far. Therefore, this study will open a new gate to expand the potential applications of COFs as exceptional piezochromic materials in pressure sensing, barcoding, and signal switching.

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