Pub Date : 2026-03-18DOI: 10.1021/acs.jpclett.5c03804
David P Hoogerheide,Sergey M Bezrukov
Motivated by the astonishingly broad spectrum of binding constants reported for interactions between peripheral proteins and membranes, we investigate possible reasons by analyzing a theoretical model of protein binding that involves seven identical contacts with the membrane surface. We demonstrate that, depending on the experimental design, the multiplicity of weak binding interactions can cause significant stretching of the binding curves. In the case of lipid surface titration by the excess of free protein in the bulk, this may result in "logarithmic binding", wherein the amount of bound protein is roughly proportional to a logarithm of its bulk concentration within many orders of magnitude. The origin of this logarithmic dependence is a gradual decrease in the average number of available contacts, accompanied by a corresponding redistribution of active contacts in the bound protein population, as the surface density of protein increases. We also show that the unbinding kinetics are described by stretched exponentials.
{"title":"Logarithmic Binding and Stretched-Exponential Kinetics in Peripheral Protein Interactions with Lipid Membrane Surfaces.","authors":"David P Hoogerheide,Sergey M Bezrukov","doi":"10.1021/acs.jpclett.5c03804","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03804","url":null,"abstract":"Motivated by the astonishingly broad spectrum of binding constants reported for interactions between peripheral proteins and membranes, we investigate possible reasons by analyzing a theoretical model of protein binding that involves seven identical contacts with the membrane surface. We demonstrate that, depending on the experimental design, the multiplicity of weak binding interactions can cause significant stretching of the binding curves. In the case of lipid surface titration by the excess of free protein in the bulk, this may result in \"logarithmic binding\", wherein the amount of bound protein is roughly proportional to a logarithm of its bulk concentration within many orders of magnitude. The origin of this logarithmic dependence is a gradual decrease in the average number of available contacts, accompanied by a corresponding redistribution of active contacts in the bound protein population, as the surface density of protein increases. We also show that the unbinding kinetics are described by stretched exponentials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471701","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 : 2026-03-18DOI: 10.1021/acs.jpclett.6c00511
Yuchong Kang,Jian Yuan,Shunwei Yao,Yilimiranmu Rouzhahong,Xiang Chen,Jin Zhang,Biao Wang,Huashan Li
While all-optical control of magnetism offers great potential for developing ultrafast spintronic devices, achieving rapid generation of transient magnetic states with long-term stability remains a significant challenge. Here, we propose that the relaxation of photoexcited electrons in a type-II spin-antiparallel heterostructure can give rise to multiple stable magnetic states. Photoinduced spin-dynamics simulations of the CrI3/CrBr3 heterostructure reveal an ultrafast phase transition from the antiferromagnetic (AFM) to the ferrimagnetic (FiM) state within 826 fs. The relaxation pathways and rates are found to be critically determined by the competition between electron-phonon coupling (EPC) and spin-orbit coupling (SOC). When electrons are initially excited to higher-energy states, both EPC and SOC strengths are enhanced 3-fold, thereby accelerating the phase transition to 346 fs. These findings advance our understanding of the dynamic coupling among spin, charge, and lattice degrees of freedom in ultrafast magnetic order transition, paving the way for the development of advanced nonvolatile memory and neuromorphic computing systems.
{"title":"Ultrafast Magnetic Order Transition Driven by Excited-State Carrier Relaxation in Ferromagnetic Heterostructures.","authors":"Yuchong Kang,Jian Yuan,Shunwei Yao,Yilimiranmu Rouzhahong,Xiang Chen,Jin Zhang,Biao Wang,Huashan Li","doi":"10.1021/acs.jpclett.6c00511","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00511","url":null,"abstract":"While all-optical control of magnetism offers great potential for developing ultrafast spintronic devices, achieving rapid generation of transient magnetic states with long-term stability remains a significant challenge. Here, we propose that the relaxation of photoexcited electrons in a type-II spin-antiparallel heterostructure can give rise to multiple stable magnetic states. Photoinduced spin-dynamics simulations of the CrI3/CrBr3 heterostructure reveal an ultrafast phase transition from the antiferromagnetic (AFM) to the ferrimagnetic (FiM) state within 826 fs. The relaxation pathways and rates are found to be critically determined by the competition between electron-phonon coupling (EPC) and spin-orbit coupling (SOC). When electrons are initially excited to higher-energy states, both EPC and SOC strengths are enhanced 3-fold, thereby accelerating the phase transition to 346 fs. These findings advance our understanding of the dynamic coupling among spin, charge, and lattice degrees of freedom in ultrafast magnetic order transition, paving the way for the development of advanced nonvolatile memory and neuromorphic computing systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"5 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471652","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 : 2026-03-17DOI: 10.1021/acs.jpclett.5c04066
Hong-Zhen Zhong,Jing Huang,Xun Xu,Xie Zhang,Jun Kang
The long-wavelength periodic moiré potential in moiré superlattices strongly modifies electronic behavior and gives rise to correlated quantum phenomena. Recent works show that remote moiré electrostatic potentials (RMEPs) allow moiré superlattices to be created in untwisted two-dimensional materials. Achieving continuous and reversible control of such RMEPs is essential for dynamic modulation of correlated states. Here, using first-principles calculations, we investigate how external pressure modulates RMEPs generated by twisted transition metal dichalcogenide bilayers. We find that pressure can significantly enhance the RMEP amplitude by 50-100%. This enhancement originates from the amplified piezocharge density caused by pressure-strengthened lattice reconstruction. These findings highlight the crucial role of the piezoelectric effect in generating the RMEPs and identify pressure as an effective method for their dynamic tuning, thereby opening new opportunities for engineering moiré superlattices and correlated quantum states.
{"title":"Pressure Enhanced Remote Moiré Electrostatic Potential in Twisted Bilayer Transition Metal Dichalcogenides.","authors":"Hong-Zhen Zhong,Jing Huang,Xun Xu,Xie Zhang,Jun Kang","doi":"10.1021/acs.jpclett.5c04066","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c04066","url":null,"abstract":"The long-wavelength periodic moiré potential in moiré superlattices strongly modifies electronic behavior and gives rise to correlated quantum phenomena. Recent works show that remote moiré electrostatic potentials (RMEPs) allow moiré superlattices to be created in untwisted two-dimensional materials. Achieving continuous and reversible control of such RMEPs is essential for dynamic modulation of correlated states. Here, using first-principles calculations, we investigate how external pressure modulates RMEPs generated by twisted transition metal dichalcogenide bilayers. We find that pressure can significantly enhance the RMEP amplitude by 50-100%. This enhancement originates from the amplified piezocharge density caused by pressure-strengthened lattice reconstruction. These findings highlight the crucial role of the piezoelectric effect in generating the RMEPs and identify pressure as an effective method for their dynamic tuning, thereby opening new opportunities for engineering moiré superlattices and correlated quantum states.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464903","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 : 2026-03-17DOI: 10.1021/acs.jpclett.6c00034
Xin Wen, Zhiyi Yao, Wenzhuo Li, Zhijun Ning, Fan Zheng
Understanding the mechanisms of UV-induced degradation is crucial for enhancing the UV stability of perovskite solar cells. The UV-driven structural dynamics of CH3NH3PbI3 (MAPbI3) are investigated using real-time TDDFT simulations, revealing that under the electron and hole excitation, the distortion of the inorganic framework is primarily driven by the electron occupation of Pb-p and I-p antibonding states, whereas in the hole case, it is mainly governed by the direct cooling induced distortion. We also found that UV accelerates the rotation of MA+ molecules. Further, a BDO molecule is introduced as a passivant, which suppresses structural distortions and provides multiphonon channels to dissipate carrier cooling energy. Experimental results confirm the UV-protective role of BDO, with suppressed PbI2 formation and improved device stability. These results clarify the mechanism of UV-induced degradation in the MAPbI3 perovskite and further elucidate how passivation molecules enhance the UV stability.
{"title":"Unraveling UV Stability in Metal Halide Perovskites: From Degradation Mechanisms to Molecular Passivation.","authors":"Xin Wen, Zhiyi Yao, Wenzhuo Li, Zhijun Ning, Fan Zheng","doi":"10.1021/acs.jpclett.6c00034","DOIUrl":"10.1021/acs.jpclett.6c00034","url":null,"abstract":"<p><p>Understanding the mechanisms of UV-induced degradation is crucial for enhancing the UV stability of perovskite solar cells. The UV-driven structural dynamics of CH<sub>3</sub>NH<sub>3</sub>PbI<sub>3</sub> (MAPbI<sub>3</sub>) are investigated using real-time TDDFT simulations, revealing that under the electron and hole excitation, the distortion of the inorganic framework is primarily driven by the electron occupation of Pb-<i>p</i> and I-<i>p</i> antibonding states, whereas in the hole case, it is mainly governed by the direct cooling induced distortion. We also found that UV accelerates the rotation of MA<sup>+</sup> molecules. Further, a BDO molecule is introduced as a passivant, which suppresses structural distortions and provides multiphonon channels to dissipate carrier cooling energy. Experimental results confirm the UV-protective role of BDO, with suppressed PbI<sub>2</sub> formation and improved device stability. These results clarify the mechanism of UV-induced degradation in the MAPbI<sub>3</sub> perovskite and further elucidate how passivation molecules enhance the UV stability.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471871","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 : 2026-03-17DOI: 10.1021/acs.jpclett.6c00344
Liangqin Zeng,Haimao Zhu,Bingqing Li,Qiusong Chen,Qiaoming Zhang,Yanlian Lei
Schottky-barrier vertical organic field-effect transistors (SB-VOFETs) provide exceptional current densities and vertical integration through gate-modulated Schottky injection. However, conventional characterization methods have limited our understanding of their full operational envelope and inherent hybrid transistor-diode nature. In this work, we conduct comprehensive bias characterization across all operational regimes with SB-VOFET featuring nanoporous silver source electrodes. Our findings demonstrate that in addition to standard transistor operation the device acts as a gate-tunable Schottky diode over a broad voltage range, a behavior often overlooked. To explain this, we propose a hybrid dual-path model that encompasses gate-insensitive I-type and gate-tunable L-type currents, which is validated by technology computer-aided design simulations. By leveraging this gate-programmability, we demonstrate a reconfigurable rectifier within a single device, enabling dynamic switching between rectification and quasi-ohmic conduction. This work broadens the characterization perspective and unlocks the latent multifunctionality of SB-VOFETs for next-generation organic electronics.
{"title":"Multi-Mode Operation and Reconfigurable Rectification in Schottky-Barrier Vertical Organic Transistors.","authors":"Liangqin Zeng,Haimao Zhu,Bingqing Li,Qiusong Chen,Qiaoming Zhang,Yanlian Lei","doi":"10.1021/acs.jpclett.6c00344","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00344","url":null,"abstract":"Schottky-barrier vertical organic field-effect transistors (SB-VOFETs) provide exceptional current densities and vertical integration through gate-modulated Schottky injection. However, conventional characterization methods have limited our understanding of their full operational envelope and inherent hybrid transistor-diode nature. In this work, we conduct comprehensive bias characterization across all operational regimes with SB-VOFET featuring nanoporous silver source electrodes. Our findings demonstrate that in addition to standard transistor operation the device acts as a gate-tunable Schottky diode over a broad voltage range, a behavior often overlooked. To explain this, we propose a hybrid dual-path model that encompasses gate-insensitive I-type and gate-tunable L-type currents, which is validated by technology computer-aided design simulations. By leveraging this gate-programmability, we demonstrate a reconfigurable rectifier within a single device, enabling dynamic switching between rectification and quasi-ohmic conduction. This work broadens the characterization perspective and unlocks the latent multifunctionality of SB-VOFETs for next-generation organic electronics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"1 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471711","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 : 2026-03-17DOI: 10.1021/acs.jpclett.6c00385
Jia Li,Yujie Yang,Shuqin Xiong,Jiayang Jiang,Yali Yu,Feng Teng,Yufeng Hu
Interfacial charge transfer in composite semiconductor channels provides a powerful and physically transparent route to achieving broadband and high-gain phototransistors, yet remains insufficiently explored in indium-free oxide-organic systems. Here, we report a broadband-responsive hybrid phototransistor based on an all-solution-processed composite channel composed of zinc-tin oxide (ZTO) and an organic bulk heterojunction PM6:Y6. In this architecture, amorphous ZTO serves primarily as a high-mobility, low-noise electron transport channel with excellent gate controllability, while the PM6:Y6 bulk heterojunction supplies strong and broadband optical absorption, enabling efficient photocarrier generation from the ultraviolet to the near-infrared region. Efficient interfacial charge transfer at the oxide/organic interface allows photogenerated electrons in the PM6:Y6 layer to be injected into the ZTO channel, where they are rapidly transported and amplified by the field-effect conduction pathway. Systematic optoelectronic characterizations reveal that the resulting high gain originates from interfacial carrier separation and accumulation at the composite channel, rather than from direct charge transport within the organic layer alone. As a result, the device exhibits pronounced photocurrent enhancement across the ultraviolet-visible-near-infrared spectral range, with a photosensitivity exceeding 5 orders of magnitude, a maximum responsivity of 9.13 × 103 A/W, and a specific detectivity on the order of 1015 Jones. By replacing indium-containing oxides with solution-processed ZTO, this work demonstrates that broadband high-gain photodetection can be realized without relying on indium-specific electronic properties. These results establish interfacial charge transfer as a general and scalable physical mechanism for designing indium-free, broadband, and high-performance oxide-based phototransistors.
复合半导体通道中的界面电荷转移为实现宽带和高增益光电晶体管提供了一条强大且物理透明的途径，但在无铟氧化有机系统中仍未得到充分探索。在这里，我们报道了一种基于锌锡氧化物（ZTO）和有机体异质结PM6:Y6组成的全溶液处理复合通道的宽带响应混合光电晶体管。在这种结构中，无定形ZTO主要作为高迁移率、低噪声的电子传输通道，具有优异的栅极可控性，而PM6:Y6体异质结提供强的宽带光吸收，实现从紫外到近红外区域的高效光载流子生成。氧化物/有机界面的高效界面电荷转移允许PM6:Y6层中的光生电子注入到ZTO通道中，在那里它们通过场效应传导途径快速传输和放大。系统的光电特性表明，所产生的高增益源于复合通道的界面载流子分离和积累，而不是仅仅来自有机层内的直接电荷传输。结果表明，该器件在紫外-可见-近红外光谱范围内表现出明显的光电流增强，光敏度超过5个数量级，最大响应率为9.13 × 103 a /W，比探测率为1015琼斯数量级。通过用溶液处理的ZTO取代含铟氧化物，这项工作表明，可以实现宽带高增益光探测，而不依赖于铟特有的电子特性。这些结果建立了界面电荷转移作为设计无铟、宽带和高性能氧化物基光电晶体管的通用和可扩展的物理机制。
{"title":"Broadband High-Gain Phototransistors Enabled by Interfacial Charge Transfer in ZTO/PM6:Y6 Composite Channels.","authors":"Jia Li,Yujie Yang,Shuqin Xiong,Jiayang Jiang,Yali Yu,Feng Teng,Yufeng Hu","doi":"10.1021/acs.jpclett.6c00385","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00385","url":null,"abstract":"Interfacial charge transfer in composite semiconductor channels provides a powerful and physically transparent route to achieving broadband and high-gain phototransistors, yet remains insufficiently explored in indium-free oxide-organic systems. Here, we report a broadband-responsive hybrid phototransistor based on an all-solution-processed composite channel composed of zinc-tin oxide (ZTO) and an organic bulk heterojunction PM6:Y6. In this architecture, amorphous ZTO serves primarily as a high-mobility, low-noise electron transport channel with excellent gate controllability, while the PM6:Y6 bulk heterojunction supplies strong and broadband optical absorption, enabling efficient photocarrier generation from the ultraviolet to the near-infrared region. Efficient interfacial charge transfer at the oxide/organic interface allows photogenerated electrons in the PM6:Y6 layer to be injected into the ZTO channel, where they are rapidly transported and amplified by the field-effect conduction pathway. Systematic optoelectronic characterizations reveal that the resulting high gain originates from interfacial carrier separation and accumulation at the composite channel, rather than from direct charge transport within the organic layer alone. As a result, the device exhibits pronounced photocurrent enhancement across the ultraviolet-visible-near-infrared spectral range, with a photosensitivity exceeding 5 orders of magnitude, a maximum responsivity of 9.13 × 103 A/W, and a specific detectivity on the order of 1015 Jones. By replacing indium-containing oxides with solution-processed ZTO, this work demonstrates that broadband high-gain photodetection can be realized without relying on indium-specific electronic properties. These results establish interfacial charge transfer as a general and scalable physical mechanism for designing indium-free, broadband, and high-performance oxide-based phototransistors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465431","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 : 2026-03-17DOI: 10.1021/acs.jpclett.6c00209
Pei-Jia Hu,Jin-Ting Ding,Irfan Hussain Bhat,Xiao-Feng Chen,Tie-Feng Fang,Ai-Min Guo,Qing-Feng Sun
Helicenes, characterized by intrinsic chiral geometry and mechanical flexibility, provide a promising organic platform for hosting and manipulating quantum states. By combining tight-binding modeling with topological band theory, we demonstrate that topologically nontrivial phases can emerge in helicenes in the presence of a gate electric field perpendicular to the molecular helix axis, as manifested by topological end states and large gap Chern numbers. In particular, the interplay between the gate electric field and mechanical strain yields rich topological phase diagrams, originating from the intrinsically coupled two-chain structure of helicenes, where the distinct electronic responses of the inner and outer chains to external perturbations lead to intricate gap overlap and band hybridization. Our work establishes helicenes as a versatile class of tunable topological materials with considerable potential for applications in molecular electronics and quantum devices.
{"title":"Topologically Nontrivial Phase and Phase Transition in Helicenes Induced by Gate Electric Field and Mechanical Strain.","authors":"Pei-Jia Hu,Jin-Ting Ding,Irfan Hussain Bhat,Xiao-Feng Chen,Tie-Feng Fang,Ai-Min Guo,Qing-Feng Sun","doi":"10.1021/acs.jpclett.6c00209","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00209","url":null,"abstract":"Helicenes, characterized by intrinsic chiral geometry and mechanical flexibility, provide a promising organic platform for hosting and manipulating quantum states. By combining tight-binding modeling with topological band theory, we demonstrate that topologically nontrivial phases can emerge in helicenes in the presence of a gate electric field perpendicular to the molecular helix axis, as manifested by topological end states and large gap Chern numbers. In particular, the interplay between the gate electric field and mechanical strain yields rich topological phase diagrams, originating from the intrinsically coupled two-chain structure of helicenes, where the distinct electronic responses of the inner and outer chains to external perturbations lead to intricate gap overlap and band hybridization. Our work establishes helicenes as a versatile class of tunable topological materials with considerable potential for applications in molecular electronics and quantum devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471708","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 : 2026-03-17DOI: 10.1021/acs.jpclett.6c00260
Jie Ma,Tianle Liu,Zhengzheng Dang,Yanming Wang,Yuljae Cho
Quasi-two-dimensional (Q2D) metal halide perovskites (PVSKs) have attracted great attention due to their improved environmental stability over three-dimensional ones. However, solution-based synthesis commonly yields mixed phases in the PVSKs that introduce an energetic disorder, limiting efficient carrier transport and thus device performance. In spite of its high demand, achieving phase-pure Q2D PVSKs remains challenging particularly for highly hydrophobic spacers due to supersaturation at the liquid-air interface and uncontrolled nucleation during crystallization. Here, we report a cosolvent-controlled crystallization method via an aqueous route, enabling the synthesis of phase-pure Q2D PVSKs single crystals based on 2-thiophenemethylammonium (TMA) with n = 1-3. Introducing sulfolane as the cosolvent increases the solubility of TMA and reduces the surface excess concentration of PVSK precursors, suppressing supersaturation and random nucleation. As a result, we obtain highly crystalline, phase-pure Q2D PVSK single crystals, confirmed by PL, XRD, and single-crystal XRD. Photodetectors fabricated from the phase-pure crystals exhibit low dark current, a high on/off ratio, high responsivity, high specific detectivity, and fast rise and fall time. This work establishes an effective strategy to overcome spacer-induced phase inhomogeneity and expands the library of phase-pure Q2D PVSKs for stable, high-performance optoelectronics.
{"title":"Phase-Pure Thiophene-Based Quasi-2D Perovskite Single Crystals via Cosolvent-Controlled Crystallization.","authors":"Jie Ma,Tianle Liu,Zhengzheng Dang,Yanming Wang,Yuljae Cho","doi":"10.1021/acs.jpclett.6c00260","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00260","url":null,"abstract":"Quasi-two-dimensional (Q2D) metal halide perovskites (PVSKs) have attracted great attention due to their improved environmental stability over three-dimensional ones. However, solution-based synthesis commonly yields mixed phases in the PVSKs that introduce an energetic disorder, limiting efficient carrier transport and thus device performance. In spite of its high demand, achieving phase-pure Q2D PVSKs remains challenging particularly for highly hydrophobic spacers due to supersaturation at the liquid-air interface and uncontrolled nucleation during crystallization. Here, we report a cosolvent-controlled crystallization method via an aqueous route, enabling the synthesis of phase-pure Q2D PVSKs single crystals based on 2-thiophenemethylammonium (TMA) with n = 1-3. Introducing sulfolane as the cosolvent increases the solubility of TMA and reduces the surface excess concentration of PVSK precursors, suppressing supersaturation and random nucleation. As a result, we obtain highly crystalline, phase-pure Q2D PVSK single crystals, confirmed by PL, XRD, and single-crystal XRD. Photodetectors fabricated from the phase-pure crystals exhibit low dark current, a high on/off ratio, high responsivity, high specific detectivity, and fast rise and fall time. This work establishes an effective strategy to overcome spacer-induced phase inhomogeneity and expands the library of phase-pure Q2D PVSKs for stable, high-performance optoelectronics.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"213 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471700","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 : 2026-03-16DOI: 10.1021/acs.jpclett.6c00414
Yuming Shu, Hanghang Lei, Qing Pan, Wanyi Zhang, Shuang Yang, Guoqiang Zou, Hongshuai Hou, Wentao Deng, Di Chen, Xiaobo Ji
The practical reversibility of Li–O2 batteries is constrained by the electronically insulating discharge product Li2O2, which limits interfacial reaction kinetics, induces large charge polarization, and accelerates electrolyte decomposition. Here we introduce Pr(NO3)3 as an electrolyte additive to generate in situ an amorphous, three-dimensional PrOx framework on a Co3O4/CNT cathode during the first discharge. This framework confines Li2O2 growth to produce nanosized, poorly ordered Li2O2 and, at the same time, provides abundant active sites and continuous electron pathways for O2 redox and Li2O2 formation/decomposition. As a result, the voltage gap decreases from 1.66 to 1.16 V at 200 μA cm–2 under a limited capacity of 400 μAh cm–2. The lowered charging potential also suppresses Li2CO3 formation, leading to an improved cycling stability.
{"title":"In Situ PrOx Framework Enables Reversible Reaction Pathways in Li–O2 Batteries","authors":"Yuming Shu, Hanghang Lei, Qing Pan, Wanyi Zhang, Shuang Yang, Guoqiang Zou, Hongshuai Hou, Wentao Deng, Di Chen, Xiaobo Ji","doi":"10.1021/acs.jpclett.6c00414","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00414","url":null,"abstract":"The practical reversibility of Li–O<sub>2</sub> batteries is constrained by the electronically insulating discharge product Li<sub>2</sub>O<sub>2</sub>, which limits interfacial reaction kinetics, induces large charge polarization, and accelerates electrolyte decomposition. Here we introduce Pr(NO<sub>3</sub>)<sub>3</sub> as an electrolyte additive to generate in situ an amorphous, three-dimensional PrO<sub><i>x</i></sub> framework on a Co<sub>3</sub>O<sub>4</sub>/CNT cathode during the first discharge. This framework confines Li<sub>2</sub>O<sub>2</sub> growth to produce nanosized, poorly ordered Li<sub>2</sub>O<sub>2</sub> and, at the same time, provides abundant active sites and continuous electron pathways for O<sub>2</sub> redox and Li<sub>2</sub>O<sub>2</sub> formation/decomposition. As a result, the voltage gap decreases from 1.66 to 1.16 V at 200 μA cm<sup>–2</sup> under a limited capacity of 400 μAh cm<sup>–2</sup>. The lowered charging potential also suppresses Li<sub>2</sub>CO<sub>3</sub> formation, leading to an improved cycling stability.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"31 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461849","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 : 2026-03-16DOI: 10.1021/acs.jpclett.6c00561
Sumit Sahu, Berk Delibas, Jahan M. Dawlaty
Controlling chemical reactivity by engineering the immediate electrostatic and solvation microenvironment of a reactant is a central goal of chemistry. Crown ethers covalently attached to reactive centers have emerged as a versatile supramolecular motif for modulating reactivity by selectively positioning metal ions near functional groups and generating localized electrostatic fields without altering covalent structure. Here, we demonstrate ion-controlled modulation of acidity in an archetypal benzoic acid system covalently functionalized with a metal-binding crown ether. Experimental pKa measurements, supported by density functional theory calculations, show that encapsulated metal ions act as effective electron-withdrawing units that stabilize the carboxylate conjugate base. We show that the induced acidity change depends on metal-ion identity, charge, size complementarity with crown ether, and hydration energy. This study establishes a quantitative framework for defining Hammett-like parameters for metal ions and provides design principles and limitations for controlling acid–base chemistry using crown ether motifs. More broadly, it demonstrates a general supramolecular strategy for tuning reactivity via noncovalent electrostatic effects.
{"title":"Ions as Substituents: A Supramolecular Hammett Approach for Electrostatic Control of Acidity","authors":"Sumit Sahu, Berk Delibas, Jahan M. Dawlaty","doi":"10.1021/acs.jpclett.6c00561","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c00561","url":null,"abstract":"Controlling chemical reactivity by engineering the immediate electrostatic and solvation microenvironment of a reactant is a central goal of chemistry. Crown ethers covalently attached to reactive centers have emerged as a versatile supramolecular motif for modulating reactivity by selectively positioning metal ions near functional groups and generating localized electrostatic fields without altering covalent structure. Here, we demonstrate ion-controlled modulation of acidity in an archetypal benzoic acid system covalently functionalized with a metal-binding crown ether. Experimental p<i>K</i><sub>a</sub> measurements, supported by density functional theory calculations, show that encapsulated metal ions act as effective electron-withdrawing units that stabilize the carboxylate conjugate base. We show that the induced acidity change depends on metal-ion identity, charge, size complementarity with crown ether, and hydration energy. This study establishes a quantitative framework for defining Hammett-like parameters for metal ions and provides design principles and limitations for controlling acid–base chemistry using crown ether motifs. More broadly, it demonstrates a general supramolecular strategy for tuning reactivity via noncovalent electrostatic effects.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"308 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-03-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147461850","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：