Pub Date : 2025-04-22DOI: 10.1021/acs.jpclett.5c00978
Prakriti Kayastha, Erik Fransson, Paul Erhart, Lucy Whalley
Correction to Octahedral Tilt-Driven Phase Transitions inBaZrS3Chalcogenide. Published in The Journal of Physical ChemistryLetters2025, 16(8), 2064–2071. The placements of the inset crystal structures in Figure 1a and Figure 1b are incorrect. They should be displayed as shown in the corrected Figure 1 below. Figure 1. DFT-calculated crystal and phonon band structures of the (a) orthorhombic Pnma (b) and cubic Pm3̅m phases. Green, gray, and yellow spheres represent Ba, Zr, and S atoms, respectively. In the Discussion we have misspelt an author name; the in-text citation to Reference 32 should read “Jaiswal et al.”. This article has not yet been cited by other publications.
{"title":"Correction to “Octahedral Tilt-Driven Phase Transitions in BaZrS3 Chalcogenide Perovskite”","authors":"Prakriti Kayastha, Erik Fransson, Paul Erhart, Lucy Whalley","doi":"10.1021/acs.jpclett.5c00978","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00978","url":null,"abstract":"Correction to <i>Octahedral Tilt-Driven Phase Transitions in</i> <i>BaZrS</i><sub>3</sub> <i>Chalcogenide</i>. Published in <cite><i>The Journal of Physical Chemistry\u0000Letters</i></cite> <span>2025</span>, <em>16</em>(8), 2064–2071. The placements of the inset crystal structures in Figure 1a and Figure 1b are incorrect. They should be displayed as shown in the corrected Figure 1 below. Figure 1. DFT-calculated crystal and phonon band structures of the (a) orthorhombic <i>Pnma</i> (b) and cubic <i>Pm</i>3̅<i>m</i> phases. Green, gray, and yellow spheres represent Ba, Zr, and S atoms, respectively. In the Discussion we have misspelt an author name; the in-text citation to Reference 32 should read “Jaiswal et al.”. This article has not yet been cited by other publications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although exciplexes with thermally activated delayed fluorescence (TADF) properties have been applied in high-efficiency organic electroluminescent devices, the development of exciplexes has been hindered due to the limited material systems and unclear formation mechanisms. Inspired by the unusual exciplex emission discovered in the pyridine solution of 2,12-di-tert-butyl-5,9-dithia-13b-boranaphtho[3,2,1-de]anthracene (TSBA) in this work, the formation mechanism of exciplexes based on two groups of pyridine-based derivative isomeric acceptors 26DCzPPy, 35DCzPPy and B2PyPB, B3PyPB and B4PyPB was explored accordingly. The difference in the position of the substituted pyridine in the isomeric acceptors can effectively regulate the formation of intramolecular N···H hydrogen bonds, which further affects their interaction with the electron-donating unit in TSBA through a conformational locking effect-induced topological rigidification of the molecule, ultimately determining the formation of the exciplex. Based on this mechanism, 35DCzPPy, B3PyPB and B4PyPB acceptors, combined with the TSBA donor, display TADF exciplex emission as expected. Among these, 35DCzPPy:TSBA shows the excellent TADF property with a high photoluminescent quantum yield reaching 78%, and the corresponding device achieves a high external quantum efficiency of 18.72% along with a small efficiency roll-off. An in-depth investigation into the influence mechanisms of intramolecular interactions on exciplex construction in this work will provide crucial theoretical guidance and design strategies for developing novel, highly efficient exciplex materials.
{"title":"Intramolecular Hydrogen Bond Modulated the Formation of Exciplex for Highly Efficient Organic Light-Emitting Diodes","authors":"Shaogang Shen, Zhi Pang, Honglei Gao, Xin Xie, Xinyi Lv, Jianjun Liu, Ying Wang","doi":"10.1021/acs.jpclett.5c00876","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00876","url":null,"abstract":"Although exciplexes with thermally activated delayed fluorescence (TADF) properties have been applied in high-efficiency organic electroluminescent devices, the development of exciplexes has been hindered due to the limited material systems and unclear formation mechanisms. Inspired by the unusual exciplex emission discovered in the pyridine solution of 2,12-di-<i>tert</i>-butyl-5,9-dithia-13b-boranaphtho[3,2,1-de]anthracene (TSBA) in this work, the formation mechanism of exciplexes based on two groups of pyridine-based derivative isomeric acceptors 26DCzPPy, 35DCzPPy and B2PyPB, B3PyPB and B4PyPB was explored accordingly. The difference in the position of the substituted pyridine in the isomeric acceptors can effectively regulate the formation of intramolecular N···H hydrogen bonds, which further affects their interaction with the electron-donating unit in TSBA through a conformational locking effect-induced topological rigidification of the molecule, ultimately determining the formation of the exciplex. Based on this mechanism, 35DCzPPy, B3PyPB and B4PyPB acceptors, combined with the TSBA donor, display TADF exciplex emission as expected. Among these, 35DCzPPy:TSBA shows the excellent TADF property with a high photoluminescent quantum yield reaching 78%, and the corresponding device achieves a high external quantum efficiency of 18.72% along with a small efficiency roll-off. An in-depth investigation into the influence mechanisms of intramolecular interactions on exciplex construction in this work will provide crucial theoretical guidance and design strategies for developing novel, highly efficient exciplex materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"108 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858224","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-22DOI: 10.1021/acs.jpclett.5c00096
Jianlong Kang, Li Zhou, Yiduo Wang, Jie Zhang, Quan Long, Xianming Zhong, Xin Li, Yingwei Wang, Si Xiao, Jun He
van der Waals crystal NbOCl2 has attracted considerable interest owing to its spontaneous parametric downconversion properties, but challenges remain due to its degradation and reduced optical nonlinearity under ambient conditions. Here, we show that high-temperature vacuum annealing can recover and even enhance second harmonic generation (SHG) in degraded NbOCl2 via recrystallization. During degradation, the second-order nonlinearity decreases, accompanied by changes in the crystal structure of NbOCl2. However, after annealing, SHG is recovered and even improved as a result of recrystallization of the degraded NbOCl2 nanosheets. This strategy enables the realization of tunable nonlinear optical responses, including harmonic generation and nonlinear absorption. By combining linear absorption spectroscopy, transient absorption, and transmission electron microscopy, we show that recrystallization occurs under specific annealing temperatures, leading to bandgap modulation and altered electronic relaxation. This study offers a new approach to achieving tunable and reversible optical nonlinearity for nonlinear optical device applications.
{"title":"Recrystallization-Driven High-Performance Optical Nonlinearity Recovery of Layered van der Waals NbOCl2","authors":"Jianlong Kang, Li Zhou, Yiduo Wang, Jie Zhang, Quan Long, Xianming Zhong, Xin Li, Yingwei Wang, Si Xiao, Jun He","doi":"10.1021/acs.jpclett.5c00096","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00096","url":null,"abstract":"van der Waals crystal NbOCl<sub>2</sub> has attracted considerable interest owing to its spontaneous parametric downconversion properties, but challenges remain due to its degradation and reduced optical nonlinearity under ambient conditions. Here, we show that high-temperature vacuum annealing can recover and even enhance second harmonic generation (SHG) in degraded NbOCl<sub>2</sub> via recrystallization. During degradation, the second-order nonlinearity decreases, accompanied by changes in the crystal structure of NbOCl<sub>2</sub>. However, after annealing, SHG is recovered and even improved as a result of recrystallization of the degraded NbOCl<sub>2</sub> nanosheets. This strategy enables the realization of tunable nonlinear optical responses, including harmonic generation and nonlinear absorption. By combining linear absorption spectroscopy, transient absorption, and transmission electron microscopy, we show that recrystallization occurs under specific annealing temperatures, leading to bandgap modulation and altered electronic relaxation. This study offers a new approach to achieving tunable and reversible optical nonlinearity for nonlinear optical device applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858222","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpclett.4c03033
Juan Bisquert
Published as part of <i>The Journal of Physical Chemistry Letters</i> special issue “Materials, Physics, and Chemistry of Neuromorphic Computing Systems”. In the era of artificial intelligence (AI), the rapid growth of unstructured data has created an urgent need for efficient, high-speed data processing and analysis. Traditional computing systems, rooted in the von Neumann architecture, struggle to keep pace due to inherent limitations, including restricted computational speed and increasing energy consumption. These challenges stem from the separation of processing and memory units, a problem known as the von Neumann bottleneck. To address these issues, researchers have turned to neuromorphic computing, which draws inspiration from the brain’s ability to perform parallel, energy-efficient operations with remarkable processing power and adaptability. Within the field of AI, notable examples of brain-inspired advances include artificial neural networks (ANNs) and deep learning (DL) neural networks, which are ANNs with several layers that lend themselves to learned feature representations. These have surpassed humans on many tasks such as pattern recognition, game playing, machine translation, and more. The algorithms are adapted to an ever-increasing range of machine learning (ML) tasks. Spiking neural networks (SNN) are of high current interest, both from the perspective of modeling neural networks of the brain and for exporting their fast-learning capability and energy efficiency into neuromorphic hardware. The goal of neuromorphic computational systems is a powerful advancement in technology that allows devices to gather data, analyze it in real time, and autonomously take actions based on the information received. A similar concept can be found in sensor computing, where sensors not only detect stimuli but also perform data conversion and processing at the point of data collection. This capability, known as in-sensor computing, reduces the need for extensive data transfer and system complexity, allowing connected devices to process information and make decisions locally─at the edge─rather than relying on a centralized system. By enabling faster, more intelligent decision-making at the edge, neuromorphic computing can transform industries and pave the way for a more connected, efficient, and intelligent future across numerous sectors, including healthcare, agriculture, manufacturing, and smart cities. Here we present the special issue Materials, Physics and Chemistry of Neuromorphic Computing Systems. There is considerable interest in attaining memory and computation functionalities based on a neurological understanding of physical and chemical phenomena, faithfully replicated in suitable devices, by detailed control of materials and surface properties at the micro- and nanoscale. Such types of functionalities can be defined by the physical chemistry analysis of different materials properties, to reproduce biological properties such as synapti
{"title":"Materials, Physics, and Chemistry of Neuromorphic Computing Systems","authors":"Juan Bisquert","doi":"10.1021/acs.jpclett.4c03033","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03033","url":null,"abstract":"Published as part of <i>The Journal of Physical Chemistry Letters</i> special issue “Materials, Physics, and Chemistry of Neuromorphic Computing Systems”. In the era of artificial intelligence (AI), the rapid growth of unstructured data has created an urgent need for efficient, high-speed data processing and analysis. Traditional computing systems, rooted in the von Neumann architecture, struggle to keep pace due to inherent limitations, including restricted computational speed and increasing energy consumption. These challenges stem from the separation of processing and memory units, a problem known as the von Neumann bottleneck. To address these issues, researchers have turned to neuromorphic computing, which draws inspiration from the brain’s ability to perform parallel, energy-efficient operations with remarkable processing power and adaptability. Within the field of AI, notable examples of brain-inspired advances include artificial neural networks (ANNs) and deep learning (DL) neural networks, which are ANNs with several layers that lend themselves to learned feature representations. These have surpassed humans on many tasks such as pattern recognition, game playing, machine translation, and more. The algorithms are adapted to an ever-increasing range of machine learning (ML) tasks. Spiking neural networks (SNN) are of high current interest, both from the perspective of modeling neural networks of the brain and for exporting their fast-learning capability and energy efficiency into neuromorphic hardware. The goal of neuromorphic computational systems is a powerful advancement in technology that allows devices to gather data, analyze it in real time, and autonomously take actions based on the information received. A similar concept can be found in sensor computing, where sensors not only detect stimuli but also perform data conversion and processing at the point of data collection. This capability, known as in-sensor computing, reduces the need for extensive data transfer and system complexity, allowing connected devices to process information and make decisions locally─at the edge─rather than relying on a centralized system. By enabling faster, more intelligent decision-making at the edge, neuromorphic computing can transform industries and pave the way for a more connected, efficient, and intelligent future across numerous sectors, including healthcare, agriculture, manufacturing, and smart cities. Here we present the special issue Materials, Physics and Chemistry of Neuromorphic Computing Systems. There is considerable interest in attaining memory and computation functionalities based on a neurological understanding of physical and chemical phenomena, faithfully replicated in suitable devices, by detailed control of materials and surface properties at the micro- and nanoscale. Such types of functionalities can be defined by the physical chemistry analysis of different materials properties, to reproduce biological properties such as synapti","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpclett.5c00633
Hongqiang Luo, Sijia Zhou, Lihua Lu, Zhongli Guo, Shanshan Zhao, Jianfeng Du, Yikai Yun, Mengyu Chen, Cheng Li
Halide perovskite memristors are rapidly emerging as promising candidates in the fields of neural network construction, logic operation, and biological synaptic simulation. Understanding the resistive switching mechanism, yet, is crucial for ensuring the stability and reproducibility of device performance. Here, we prepare quasi-2D perovskites with enhanced performance through the optimization of molecular, solvents, and dimensions. Subsequently, the switching process of the quasi-2D perovskite memristors is directly observed by a nondestructive in situ photoluminescence (PL) imaging microscope. In addition, the elemental composition of the conductive filaments (CFs) is analyzed, showing that devices with active metal top electrodes allow the presence of both active metal CFs and halogen vacancy CFs during the resistive switching process. This work provides valuable insights into the switching mechanisms of quasi-2D perovskite memristors and enhances the prospects for their applications.
{"title":"Mechanistic Insights into the Resistive Switching Mechanism of Quasi-2D Perovskite Memristors","authors":"Hongqiang Luo, Sijia Zhou, Lihua Lu, Zhongli Guo, Shanshan Zhao, Jianfeng Du, Yikai Yun, Mengyu Chen, Cheng Li","doi":"10.1021/acs.jpclett.5c00633","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00633","url":null,"abstract":"Halide perovskite memristors are rapidly emerging as promising candidates in the fields of neural network construction, logic operation, and biological synaptic simulation. Understanding the resistive switching mechanism, yet, is crucial for ensuring the stability and reproducibility of device performance. Here, we prepare quasi-2D perovskites with enhanced performance through the optimization of molecular, solvents, and dimensions. Subsequently, the switching process of the quasi-2D perovskite memristors is directly observed by a nondestructive <i>in situ</i> photoluminescence (PL) imaging microscope. In addition, the elemental composition of the conductive filaments (CFs) is analyzed, showing that devices with active metal top electrodes allow the presence of both active metal CFs and halogen vacancy CFs during the resistive switching process. This work provides valuable insights into the switching mechanisms of quasi-2D perovskite memristors and enhances the prospects for their applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"45 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853380","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpclett.5c00746
Victor M. Freixas, Nicolas Oldani, Laura Alfonso-Hernandez, Dianelys Ondarse-Alvarez, Hassiel Negrin-Yuvero, Johan Fabian Galindo, Sergei Tretiak, Sebastian Fernandez-Alberti
The synthesis of novel carbon nanostructures with unique topologies expands the landscape of organic molecules, introducing new chemical properties and potential applications. Carbon nanorings, composed of cyclic paraphenylene (CPP) chains, serve as a versatile scaffold for designing materials with unique molecular architectures that impact their optical properties and photoinduced dynamics. These new topologies alter the balance between competing π-conjugation effects, high bending strain energies, and steric hindrances imposed by the rearrangement of their cyclic structures. Here, we explore the photoinduced dynamics of the all-benzene trefoil knot using nonadiabatic excited-state molecular dynamics. We show how its absorption spectra can be modeled by a particle in a box constrained to the trefoil knot geometry, and we analyze the internal conversion process following photoexcitation. Our findings reveal an exciton intraring migration governed by the winding of the paraphenylene chain, ultimately leading to exciton self-trapping at specific high curvature regions of the knot. This behavior contrasts with the nondeterministic exciton self-trapping in the corresponding CPP, where localization occurs randomly across different phenylene units. Our results highlight the ability of molecular knots to control exciton dynamics through curvature, tension, and planarization effects, positioning these materials as promising candidates for future technological applications. This ability to precisely manipulate optical and electronic characteristics is essential for developing more efficient and versatile devices.
{"title":"Pinning Excited State Self-Trapping with All-Benzene Trefoil Knot","authors":"Victor M. Freixas, Nicolas Oldani, Laura Alfonso-Hernandez, Dianelys Ondarse-Alvarez, Hassiel Negrin-Yuvero, Johan Fabian Galindo, Sergei Tretiak, Sebastian Fernandez-Alberti","doi":"10.1021/acs.jpclett.5c00746","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00746","url":null,"abstract":"The synthesis of novel carbon nanostructures with unique topologies expands the landscape of organic molecules, introducing new chemical properties and potential applications. Carbon nanorings, composed of cyclic paraphenylene (CPP) chains, serve as a versatile scaffold for designing materials with unique molecular architectures that impact their optical properties and photoinduced dynamics. These new topologies alter the balance between competing π-conjugation effects, high bending strain energies, and steric hindrances imposed by the rearrangement of their cyclic structures. Here, we explore the photoinduced dynamics of the all-benzene trefoil knot using nonadiabatic excited-state molecular dynamics. We show how its absorption spectra can be modeled by a particle in a box constrained to the trefoil knot geometry, and we analyze the internal conversion process following photoexcitation. Our findings reveal an exciton intraring migration governed by the winding of the paraphenylene chain, ultimately leading to exciton self-trapping at specific high curvature regions of the knot. This behavior contrasts with the nondeterministic exciton self-trapping in the corresponding CPP, where localization occurs randomly across different phenylene units. Our results highlight the ability of molecular knots to control exciton dynamics through curvature, tension, and planarization effects, positioning these materials as promising candidates for future technological applications. This ability to precisely manipulate optical and electronic characteristics is essential for developing more efficient and versatile devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Graphene-based dual-atom catalysts M1/M2-N6-Gra have shown significant potential in various reactions, although their stabilities are debated. Therefore, developing an efficient and accurate approach to screen thermodynamically stable M1/M2-N6-Gra is significant. Herein, we designed a rational machine learning (ML) scheme based on 143 DFT calculated samples to predict the formation energies (Ef) of 1134 possible M1/M2-N6-Gra. A well performing multilayer perceptron model with test set R2= 0.98 was obtained after feature engineering, model training, data supplementation, and transfer learning. This model successfully screened 604 thermodynamic stable M1/M2-N6-Gra with Ef < 0 eV. Feature importance, predictions distribution, and energy decomposition revealed that the coordination number significantly influences Ef, with cohesive energy dominating low-coordination catalysts and binding energy between metal and substrate being more critical in higher-coordination catalysts. This work highlights the potential of ML and developed effective approaches to screen thermodynamically stable catalysts and reveals the laws of stability for various materials.
{"title":"Fast-Track to Catalyst Stability: Machine Learning Optimized Predictions for M1/M2-N6-Gra Catalysts","authors":"Pengxin Pu, Xin Song, Hu Ding, Yuan Deng, Haisong Feng, Xin Zhang","doi":"10.1021/acs.jpclett.5c00097","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00097","url":null,"abstract":"Graphene-based dual-atom catalysts M1/M2-N<sub>6</sub>-Gra have shown significant potential in various reactions, although their stabilities are debated. Therefore, developing an efficient and accurate approach to screen thermodynamically stable M1/M2-N<sub>6</sub>-Gra is significant. Herein, we designed a rational machine learning (ML) scheme based on 143 DFT calculated samples to predict the formation energies (<i>E</i><sub><i>f</i></sub>) of 1134 possible M1/M2-N<sub>6</sub>-Gra. A well performing multilayer perceptron model with test set <i>R</i><sup>2</sup> <i>=</i> 0.98 was obtained after feature engineering, model training, data supplementation, and transfer learning. This model successfully screened 604 thermodynamic stable M1/M2-N<sub>6</sub>-Gra with <i>E</i><sub><i>f</i></sub> < 0 eV. Feature importance, predictions distribution, and energy decomposition revealed that the coordination number significantly influences <i>E</i><sub><i>f</i></sub>, with cohesive energy dominating low-coordination catalysts and binding energy between metal and substrate being more critical in higher-coordination catalysts. This work highlights the potential of ML and developed effective approaches to screen thermodynamically stable catalysts and reveals the laws of stability for various materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"33 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143858233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpclett.5c00151
Pavel M. Talianov, Daria D. Mikushina, Sergey Rzhevskiy, Konstantin V. Arabuli, Lev E. Zelenkov, Soslan Khubezhov, Lev S. Logunov, Dmitry S. Gets, Oleksii O. Peltek, Mikhail V. Zyuzin, Sergey V. Makarov
Metal halide perovskites present a vast potential for the development of cutting-edge optoelectronic devices. However, their vulnerability to environmental factors, especially humidity, leads to widely acknowledged stability challenges. On the other hand, such a high sensitivity to water in the atmosphere is an opportunity for humidity sensing applications. In this study, we synthesize lead halide perovskite CsPbBr3 nanocrystals within CaCO3 templates with a porous structure (CsPbBr3@CaCO3) and investigate the mechanisms underlying the fluorescence response to changes in relative humidity. The reversible transformation of CsPbBr3 to CsPb2Br5 leads to the removal of surface defects, which results in an increase in photoluminescence intensity, thereby enabling the determination of ambient relative humidity levels. Moreover, we investigated a mechanism of CsPbBr3 degradation driven by CO2 in humid environments underlying the perovskite transformations. As a proof of concept, we developed a fluorescence-based humidity sensor based on CsPbBr3@CaCO3 with rapid response and recovery times, maintaining performance across multiple cycles.
{"title":"Template-Assisted Synthesis of CsPbBr3 Nanocrystals with a Humidity-Induced Fluorescent Response: Mechanism and Sensing Applications","authors":"Pavel M. Talianov, Daria D. Mikushina, Sergey Rzhevskiy, Konstantin V. Arabuli, Lev E. Zelenkov, Soslan Khubezhov, Lev S. Logunov, Dmitry S. Gets, Oleksii O. Peltek, Mikhail V. Zyuzin, Sergey V. Makarov","doi":"10.1021/acs.jpclett.5c00151","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00151","url":null,"abstract":"Metal halide perovskites present a vast potential for the development of cutting-edge optoelectronic devices. However, their vulnerability to environmental factors, especially humidity, leads to widely acknowledged stability challenges. On the other hand, such a high sensitivity to water in the atmosphere is an opportunity for humidity sensing applications. In this study, we synthesize lead halide perovskite CsPbBr<sub>3</sub> nanocrystals within CaCO<sub>3</sub> templates with a porous structure (CsPbBr<sub>3</sub>@CaCO<sub>3</sub>) and investigate the mechanisms underlying the fluorescence response to changes in relative humidity. The reversible transformation of CsPbBr<sub>3</sub> to CsPb<sub>2</sub>Br<sub>5</sub> leads to the removal of surface defects, which results in an increase in photoluminescence intensity, thereby enabling the determination of ambient relative humidity levels. Moreover, we investigated a mechanism of CsPbBr<sub>3</sub> degradation driven by CO<sub>2</sub> in humid environments underlying the perovskite transformations. As a proof of concept, we developed a fluorescence-based humidity sensor based on CsPbBr<sub>3</sub>@CaCO<sub>3</sub> with rapid response and recovery times, maintaining performance across multiple cycles.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"6 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cyanobacteriochromes are photoreceptors that constitute a significant subset of phycocyanobilin-bound proteins, yet the details of their excited-state photochemical and structural dynamics have not been fully elucidated. Here, we investigate the photoisomerization dynamics of a newly identified far-red/orange light-absorbing cyanobacteriochrome using femtosecond-resolved fluorescence and absorption methods. We observed active-site relaxations ranging from a few to hundreds of picoseconds for both far-red and orange-absorbing states. As such relaxations modulate the potential energy landscape of the chromophore, we also observed a unique dynamic spectral tuning in the far-red-absorbing state and an apparent dynamic Stokes shift in the orange-absorbing state in the femtosecond-resolved fluorescence spectra. We found that the isomerization reactions in both states occur within 320–400 ps. The observed correlation of the local relaxation and the phycocyanobilin twisting can be critical to the subsequent conformational changes after isomerization through the conical intersection to reach the final biological functions. Understanding of the time scales of the local relaxations and isomerization reactions is important to guide the design and engineering of phycocyanobilin-based light-sensitive systems of desired optical properties via synthetic biology.
{"title":"Elucidation of the Ultrafast Origin of Multiphasic Dynamics in a Far-Red-Sensing Cyanobacteriochrome","authors":"Dihao Wang, Kangwei Niu, Linta M. Biju, Lijuan Wang, Xiaojing Yang, Dongping Zhong","doi":"10.1021/acs.jpclett.5c00487","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00487","url":null,"abstract":"Cyanobacteriochromes are photoreceptors that constitute a significant subset of phycocyanobilin-bound proteins, yet the details of their excited-state photochemical and structural dynamics have not been fully elucidated. Here, we investigate the photoisomerization dynamics of a newly identified far-red/orange light-absorbing cyanobacteriochrome using femtosecond-resolved fluorescence and absorption methods. We observed active-site relaxations ranging from a few to hundreds of picoseconds for both far-red and orange-absorbing states. As such relaxations modulate the potential energy landscape of the chromophore, we also observed a unique dynamic spectral tuning in the far-red-absorbing state and an apparent dynamic Stokes shift in the orange-absorbing state in the femtosecond-resolved fluorescence spectra. We found that the isomerization reactions in both states occur within 320–400 ps. The observed correlation of the local relaxation and the phycocyanobilin twisting can be critical to the subsequent conformational changes after isomerization through the conical intersection to reach the final biological functions. Understanding of the time scales of the local relaxations and isomerization reactions is important to guide the design and engineering of phycocyanobilin-based light-sensitive systems of desired optical properties via synthetic biology.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853377","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-21DOI: 10.1021/acs.jpclett.5c00753
Teng Ji, Falong Yan, Yang Zhang, Qun Lu, Kaige Gao
Two novel one-dimensional (1D) lead halide elastic crystals, [Pb2Br4(DMA)2]n (1) (DMA = N,N-dimethylacetamide) and [Pb2Br4(DMF)2]n (2) (DMF = N,N-dimethylformamide), were reported. Both compounds 1 and 2 feature a neutral 1D bimetallic axis chain structure. The bending strain of compound 1 is 1.36%, higher than those of all reported 1D single-metal axis chain coordinate polymers, indicating the superior elastic properties of the 1D bimetallic axis chain polymers. Compound 1 exhibits strong red-to-near-infrared (NIR) fluorescence emission below 200 K, with an emission peak at 700 nm and a full width at half maximum (fwhm) of 200 nm, indicating strong electron–phonon coupling in compound 1. The large Stokes shift and broad fwhm of compound 1 may be attributed to its excellent elasticity, as this elasticity allows the molecule’s self-trapped exciton state to undergo greater structural distortion. It is suggested that 1D organic lead halide elastic crystals could be promising candidates for emerging applications in efficient NIR light-emitting diodes, supercontinuum sources, and flexible NIR optical waveguides.
{"title":"One-Dimensional Organic Lead Bromide Elastic Crystals with Strong Electron–Phonon Coupling","authors":"Teng Ji, Falong Yan, Yang Zhang, Qun Lu, Kaige Gao","doi":"10.1021/acs.jpclett.5c00753","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00753","url":null,"abstract":"Two novel one-dimensional (1D) lead halide elastic crystals, [Pb<sub>2</sub>Br<sub>4</sub>(DMA)<sub>2</sub>]<sub><i>n</i></sub> (<b>1</b>) (DMA = <i>N</i>,<i>N</i>-dimethylacetamide) and [Pb<sub>2</sub>Br<sub>4</sub>(DMF)<sub>2</sub>]<sub><i>n</i></sub> (<b>2</b>) (DMF = <i>N</i>,<i>N</i>-dimethylformamide), were reported. Both compounds <b>1</b> and <b>2</b> feature a neutral 1D bimetallic axis chain structure. The bending strain of compound <b>1</b> is 1.36%, higher than those of all reported 1D single-metal axis chain coordinate polymers, indicating the superior elastic properties of the 1D bimetallic axis chain polymers. Compound <b>1</b> exhibits strong red-to-near-infrared (NIR) fluorescence emission below 200 K, with an emission peak at 700 nm and a full width at half maximum (fwhm) of 200 nm, indicating strong electron–phonon coupling in compound <b>1</b>. The large Stokes shift and broad fwhm of compound <b>1</b> may be attributed to its excellent elasticity, as this elasticity allows the molecule’s self-trapped exciton state to undergo greater structural distortion. It is suggested that 1D organic lead halide elastic crystals could be promising candidates for emerging applications in efficient NIR light-emitting diodes, supercontinuum sources, and flexible NIR optical waveguides.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"28 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143853379","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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