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Terahertz-Raman spectroscopy for in situ benchtop monitoring of changes to extended, supramolecular structure in milling mechanochemistry 太赫兹-拉曼光谱法用于原位台式监测研磨机械化学中扩展超分子结构的变化

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.018

Tristan H. Borchers , Filip Topić , Mihails Arhangelskis , Michael Ferguson , Cameron B. Lennox , Patrick A. Julien , Tomislav Friščić

Low-frequency Raman, also known as terahertz-Raman (THz-Raman), spectroscopy offers a laboratory benchtop-based alternative to synchrotron X-ray diffraction for real-time, in situ monitoring of ball-milling mechanochemical reactions. Although direct monitoring of the long-range structure of materials during mechanochemical reactions is generally challenging by conventional Raman spectroscopy, and typically requires synchrotron X-ray diffraction, here we use THz-Raman spectroscopy to monitor mechanosynthesis of cocrystals, stoichiomorphs, and polymorphs, detect multi-step sequences, and discover solid-state phases in systems difficult to differentiate using fingerprint-region Raman spectroscopy—all through real-time observation of changes in lattice vibrational models. The methodology is augmented by periodic density functional theory (DFT), which enables structural interpretation of spectroscopic changes, notably the identification of THz-Raman bands associated with halogen bond transformations. Simultaneous monitoring of mechanochemical processes in both the fingerprint and low-frequency Raman regions enables real-time observation of changes to extended as well as molecular structure during milling, in a single laboratory benchtop experiment, without synchrotron radiation.

低频拉曼（又称太赫兹-拉曼，THz-Raman）光谱法为实验室台式同步辐射 X 射线衍射法提供了一种替代方法，可用于实时、原位监测球磨机械化学反应。虽然在机械化学反应过程中直接监测材料的长程结构通常是传统拉曼光谱法所无法实现的，而且通常需要同步辐射 X 射线衍射法，但在这里，我们使用太赫兹-拉曼光谱法监测共晶体、共晶和多晶体的机械合成，检测多步序列，并在使用指纹区拉曼光谱法难以区分的系统中发现固态相--所有这些都是通过实时观测晶格振动模型的变化实现的。周期性密度泛函理论（DFT）对该方法进行了增强，从而能够对光谱变化进行结构解释，特别是识别与卤素键转化相关的太赫兹-拉曼带。同时监测指纹区和低频拉曼区的机械化学过程，可在实验室台式实验中实时观察研磨过程中扩展分子结构的变化，而无需同步辐射。

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引用次数: 0

Anisotropy-guided interface molecular engineering for stable blue electroluminescence 各向异性引导的界面分子工程实现稳定的蓝色电致发光

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.08.019

Eunhye Hwang , Unhyeok Jo , Jiyeon Kim , Deok-Ho Roh , Seung Chan Kim , Minseok Kim , Hyun-Chul Ki , Wonyoung Choe , Jun Yeob Lee , Tae-Hyuk Kwon

Despite the emergence of interlayers with high triplet energies (T₁) to stabilize blue phosphorescent organic light-emitting diodes (PhOLEDs), a limited understanding of their molecular structures poses a challenge in preventing triplet exciton leakage while maintaining charge balance. Here, we report a rational design strategy for interlayers aimed at concurrently controlling T₁ and molecular arrangements conducive to charge transport. Four interlayer materials having high T₁ (∼3.0 eV) are developed as electron-blocking materials (EBMs), utilizing asymmetric orthogonal geometries with varying torsion angles and dipole moments. X-ray crystallographic analyses reveal that the EBM, featuring the most asymmetric charge distributions, exhibits a herringbone packing and a face-on orientation through dipole-induced anisotropic interactions, thereby promoting hole transport. The power efficiency and operational lifetime of the corresponding blue PhOLEDs increase by 24% and 21%, respectively, compared with a conventional EBM. This study offers extensive insights into designing interlayers with versatile applicability in optoelectronics harnessing triplets.

尽管出现了具有高三重态能量（T1）的中间膜来稳定蓝色磷光有机发光二极管（PhOLED），但由于对其分子结构的了解有限，在防止三重态激子泄漏同时保持电荷平衡方面面临着挑战。在此，我们报告了一种合理的夹层设计策略，旨在同时控制 T1 和有利于电荷传输的分子排列。我们利用具有不同扭转角和偶极矩的不对称正交几何结构，开发了四种具有高 T1（∼3.0 eV）的层间材料，作为电子阻挡材料（EBM）。X 射线晶体学分析表明，EBM 具有最不对称的电荷分布，通过偶极子诱导的各向异性相互作用，呈现出人字形堆积和面朝上取向，从而促进了空穴传输。与传统的 EBM 相比，相应的蓝色 PhOLED 的功率效率和工作寿命分别提高了 24% 和 21%。这项研究为在光电子学中设计具有广泛适用性的利用三胞胎的中间膜提供了广泛的启示。

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引用次数: 0

Non-fluorinated electrolytes with micelle-like solvation for ultra-high-energy-density lithium metal batteries 用于超高能量密度锂金属电池的胶束状溶解的无氟电解质

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2024.09.005

Rui Qiao , Yan Zhao , Shijie Zhou , Huijun Zhang , Fuzhu Liu , Tianhong Zhou , Baoyu Sun , Hao Fan , Chao Li , Yanhua Zhang , Feng Liu , Xiangdong Ding , Jang Wook Choi , Ali Coskun , Jiangxuan Song

Electrolyte engineering plays a critical role in enabling lithium (Li) metal batteries. However, the simultaneous realization of anion-rich solvation structure and high ionic conductivity of electrolytes via solvation structure design remains challenging. Here, we report a low-cost, non-fluorinated electrolyte with a micelle-like solvation structure by introducing amphiphilic n-butyl methyl ether (MNBE) into Li bis(fluorosulfonyl)imide (LiFSI)/1,2-dimethoxyethane (DME) for stable Li metal batteries (LMBs). MNBE can effectively promote Li⁺-FSI⁻ coordination through steric crowding. Meanwhile, the inert alkyl chains of MNBE can mitigate the reaction between electrolyte and Li metal due to their lithiophobicity. Specifically, the micelle-like, non-fluorinated electrolyte exhibits an ionic conductivity as high as 12.55 mS cm⁻¹, and its anion-rich solvation structure promotes the formation of LiF-rich solid-electrolyte interphase. We constructed a 7.3 Ah Li||NMC811 pouch cell employing this electrolyte under harsh conditions, exhibiting ultra-high specific energy of 503.7 Wh kg⁻¹ with impressive cycling stability of 84.1% capacity retention after 100 cycles.

电解质工程在实现锂（Li）金属电池方面发挥着至关重要的作用。然而，通过溶解结构设计同时实现电解质的富阴离子溶解结构和高离子电导率仍然具有挑战性。在此，我们通过在双氟磺酰亚胺锂（LiFSI）/1,2-二甲氧基乙烷（DME）中引入两亲性正丁基甲基醚（MNBE），报告了一种具有胶束状溶解结构的低成本无氟电解质，可用于制造稳定的锂金属电池（LMB）。MNBE 可通过立体拥挤有效促进 Li+-FSI- 配位。同时，MNBE 的惰性烷基链具有疏锂性，可减轻电解质与锂金属之间的反应。具体来说，胶束状非氟化电解质的离子电导率高达 12.55 mS cm-1，其富含阴离子的溶解结构促进了富含 LiF 的固体-电解质间相的形成。我们在苛刻的条件下利用这种电解质构建了一个 7.3 Ah 的锂||NMC811 袋式电池，显示出 503.7 Wh kg-1 的超高比能量和令人印象深刻的循环稳定性，100 次循环后容量保持率为 84.1%。

{"title":"Non-fluorinated electrolytes with micelle-like solvation for ultra-high-energy-density lithium metal batteries","authors":"Rui Qiao , Yan Zhao , Shijie Zhou , Huijun Zhang , Fuzhu Liu , Tianhong Zhou , Baoyu Sun , Hao Fan , Chao Li , Yanhua Zhang , Feng Liu , Xiangdong Ding , Jang Wook Choi , Ali Coskun , Jiangxuan Song","doi":"10.1016/j.chempr.2024.09.005","DOIUrl":"10.1016/j.chempr.2024.09.005","url":null,"abstract":"<div><div>Electrolyte engineering plays a critical role in enabling lithium (Li) metal batteries. However, the simultaneous realization of anion-rich solvation structure and high ionic conductivity of electrolytes via solvation structure design remains challenging. Here, we report a low-cost, non-fluorinated electrolyte with a micelle-like solvation structure by introducing amphiphilic n-butyl methyl ether (MNBE) into Li bis(fluorosulfonyl)imide (LiFSI)/1,2-dimethoxyethane (DME) for stable Li metal batteries (LMBs). MNBE can effectively promote Li+-FSI− coordination through steric crowding. Meanwhile, the inert alkyl chains of MNBE can mitigate the reaction between electrolyte and Li metal due to their lithiophobicity. Specifically, the micelle-like, non-fluorinated electrolyte exhibits an ionic conductivity as high as 12.55 mS cm−1, and its anion-rich solvation structure promotes the formation of LiF-rich solid-electrolyte interphase. We constructed a 7.3 Ah Li||NMC811 pouch cell employing this electrolyte under harsh conditions, exhibiting ultra-high specific energy of 503.7 Wh kg−1 with impressive cycling stability of 84.1% capacity retention after 100 cycles.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 2","pages":"Article 102306"},"PeriodicalIF":19.1,"publicationDate":"2025-02-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142369578","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Spectral control of photoenzyme through allosteric chromophore tuning 通过变构生色团调谐的光酶光谱控制

IF 19.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-13 DOI: 10.1016/j.chempr.2025.102430

Menghan Xu , Yuki Yamanashi , Motomu Kanai

Artificial photoenzymes offering non-natural reactivities present a promising synthetic strategy, yet the use of red light remains challenging. In this issue of Chem, Gregory D. Scholes, Sijia S. Dong, Todd K. Hyster, and coworkers reported a groundbreaking approach to engineering a photoenzyme to use red light by tuning the protein microenvironment, opening a new window for chem-bio catalysis.

提供非自然反应的人工光酶是一种很有前途的合成策略，但红光的使用仍然具有挑战性。在这一期的《化学》杂志上，Gregory D. Scholes, Sijia S. Dong, Todd K. Hyster及其同事报道了一种开创性的方法，通过调节蛋白质微环境来设计一种光酶，使其使用红光，为化学-生物催化打开了一扇新的窗口。

引用次数: 0

para-Selective C–H alkylation of aroyl chlorides through organic photoredox-catalyzed radical tele-substitution

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-12 DOI: 10.1016/j.chempr.2025.102446

Ryoto Oya, Hinata Sato, Kazunori Nagao, Hirohisa Ohmiya

The site-selective C(sp²)–H alkylation of arenes has provided ubiquitous fragments found in pharmaceutical drugs and agrochemicals. Although ortho- and meta-selective alkylation reactions have been achieved well, para-selective examples are scarce. The currently available methods have been designed on the unique behaviors and characteristics of metals to achieve high para-selectivity. Herein, we demonstrate the para-selective C(sp²)–H alkylation of aroyl chlorides with alkyltrifluoroborates and trialkylphosphine through an organic photoredox-catalyzed radical tele-substitution. The reaction proceeds through the para-selective addition of alkyl radicals to in-situ-generated aroyl trialkylphosphonium intermediates followed by a hydrogen shift. Notably, the para-alkylation is associated with the conversion of the carbonyl trialkylphosphonium group to the formyl group, producing para-alkylated benzaldehyde derivatives. This metal-free site-selective C(sp²)–C(sp³) bond formation allows for streamlined synthesis of siponimod and SR-31747.

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引用次数: 0

Reversible-deactivation radical copolymerization of tetrafluoroethylene via the formation of divergent termini in dormant chains

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-12 DOI: 10.1016/j.chempr.2025.102434

Kaixuan Chen, Zexi Zhang, Qianhao Ye, Yixuan Liu, Shantao Han, Mengli Xu, Mao Chen

Tetrafluoroethylene (TFE) is the principal monomer in fluoropolymer industries. However, difficulties in accessing well-defined structures have hampered in-depth investigation into TFE polymers. Here, we reveal the distinctive reactivity of TFE among various fluoroalkenes during the formation of dormant chains and introduce a divergent deactivation strategy for facilitating the reversible generation of different chain-end connections based on a photoorganocatalyzed reversible-deactivation radical copolymerization. This versatile approach enables the controlled synthesis of TFE copolymers with tunable molar masses (up to 211.7 kDa), various comonomer units, and block sequences with sophisticated compositions, shedding light on realizing controlled polymerization for challenging monomers. Furthermore, this synthetic breakthrough lays the groundwork for exploring the characteristics of tailor-made TFE copolymers (e.g., glass transition temperature, electrochemical stability, and viscosity), which should drive the rational design of high-performance materials.

引用次数: 0

Air-stable radical polycyclic aromatic hydrogen-bonded organic frameworks

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-12 DOI: 10.1016/j.chempr.2025.102445

Bai-Tong Liu, Tao Li, Sheng-Hao Gong, Jia-Chuan Liu, Ze-Yu Ruan, Han Han, Timothy Y.-Z. Li, Yuanning Feng, Rui Wang, Li Gong, Xieming Xu, Rong Cao, Ming-Liang Tong, J. Fraser Stoddart, Tian-Fu Liu

Air-stable radical materials have emerged as promising candidates for next-generation electronic materials. Traditionally, constructing radical materials has required the intricate design and prolonged synthesis of radical building blocks. Herein, we have discovered a group of polycyclic aromatic monomers, previously considered to be air-unstable radicals, that can be oxidized to air-stable radical materials according to a post-synthetic protocol when they are incorporated into solid porous hydrogen-bonded organic frameworks (HOFs). The inherent porosity and crystallinity of HOFs facilitate extensive interactions with redox agents, such as tetravalent cerium(IV). These radical HOF materials exhibit high radical concentrations with paramagnetic behavior equivalent to two monomers sharing an unpaired electron. The HOFs can maintain their radical nature under ambient conditions on account of spin delocalization along the [π···π] stacked units. The radical formation transforms the HOFs from insulators to typical n-type semiconductors. This discovery opens up avenues for exploring stable radical materials with diverse applications.

{"title":"Air-stable radical polycyclic aromatic hydrogen-bonded organic frameworks","authors":"Bai-Tong Liu, Tao Li, Sheng-Hao Gong, Jia-Chuan Liu, Ze-Yu Ruan, Han Han, Timothy Y.-Z. Li, Yuanning Feng, Rui Wang, Li Gong, Xieming Xu, Rong Cao, Ming-Liang Tong, J. Fraser Stoddart, Tian-Fu Liu","doi":"10.1016/j.chempr.2025.102445","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102445","url":null,"abstract":"Air-stable radical materials have emerged as promising candidates for next-generation electronic materials. Traditionally, constructing radical materials has required the intricate design and prolonged synthesis of radical building blocks. Herein, we have discovered a group of polycyclic aromatic monomers, previously considered to be air-unstable radicals, that can be oxidized to air-stable radical materials according to a post-synthetic protocol when they are incorporated into solid porous hydrogen-bonded organic frameworks (HOFs). The inherent porosity and crystallinity of HOFs facilitate extensive interactions with redox agents, such as tetravalent cerium(IV). These radical HOF materials exhibit high radical concentrations with paramagnetic behavior equivalent to two monomers sharing an unpaired electron. The HOFs can maintain their radical nature under ambient conditions on account of spin delocalization along the [π···π] stacked units. The radical formation transforms the HOFs from insulators to typical n-type semiconductors. This discovery opens up avenues for exploring stable radical materials with diverse applications.","PeriodicalId":268,"journal":{"name":"Chem","volume":"7 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Transition-path times of individual molecular shuttles under mechanical equilibrium show symmetry

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-11 DOI: 10.1016/j.chempr.2024.102410

Tomás Nicolás-García, Natalia Martín Sabanés, Rebeca Bocanegra, R. Dean Astumian, Emilio M. Pérez, Borja Ibarra

Measuring individual trajectories during the operation of synthetic devices is crucial for a thorough understanding of this operation. Here, we use optical tweezers to measure individual transition paths of molecular shuttles under mechanical equilibrium. Our results showed that the transition-path times present wide distributions, indicating a statistically independent and variable behavior while maintaining a time-reversal symmetry derived from the principle of microscopic reversibility. Furthermore, we show that thermodynamic variables can be extracted from the transition-path times using the principle of microscopic reversibility. These measurements provide a first experimental look at the principle of microscopic reversibility in molecular shuttles and pave the way for a detailed and quantitative understanding of the dynamics of synthetic molecular machines.

引用次数: 0

Recycling homocarbon backbone polymers toward a circular materials economy

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-10 DOI: 10.1016/j.chempr.2024.102406

Jie Zheng, Zhuang Mao Png, Xin Yi Oh, Huanning Zuo, Zibiao Li

Global plastic waste has reached a critical level, posing serious hazards to ecosystems and human health because of its persistent presence in landfills, oceans, and natural environments. Unlike heteroatom-backbone polymers, which feature a heterochain structure, homocarbon backbone polymers with nonpolar C–C backbones exhibit unprecedented durability and resistance to environmental factors, making them less prone to degradation. Consequently, the conversion of such plastic waste into valuable chemicals via chemical recycling presents a crucial solution to address the issues stemming from plastic waste. This review aims to summarize the latest developments in the closed-loop recycling and upcycling of homocarbon backbone polymers with a specific focus on the conversion of waste plastics into their original monomers and/or value-added chemicals through bio-, thermo-, and photocatalysis, which promotes a circular economy. Notably, the development of highly active catalysts and related depolymerization systems accelerates the evolution of plastic degradation and enhances product controllability, rendering the recycling of plastic waste feasible and affordable.

{"title":"Recycling homocarbon backbone polymers toward a circular materials economy","authors":"Jie Zheng, Zhuang Mao Png, Xin Yi Oh, Huanning Zuo, Zibiao Li","doi":"10.1016/j.chempr.2024.102406","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102406","url":null,"abstract":"Global plastic waste has reached a critical level, posing serious hazards to ecosystems and human health because of its persistent presence in landfills, oceans, and natural environments. Unlike heteroatom-backbone polymers, which feature a heterochain structure, homocarbon backbone polymers with nonpolar C–C backbones exhibit unprecedented durability and resistance to environmental factors, making them less prone to degradation. Consequently, the conversion of such plastic waste into valuable chemicals via chemical recycling presents a crucial solution to address the issues stemming from plastic waste. This review aims to summarize the latest developments in the closed-loop recycling and upcycling of homocarbon backbone polymers with a specific focus on the conversion of waste plastics into their original monomers and/or value-added chemicals through bio-, thermo-, and photocatalysis, which promotes a circular economy. Notably, the development of highly active catalysts and related depolymerization systems accelerates the evolution of plastic degradation and enhances product controllability, rendering the recycling of plastic waste feasible and affordable.","PeriodicalId":268,"journal":{"name":"Chem","volume":"51 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375294","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Design of light- and chemically responsive protein assemblies through host-guest interactions

IF 23.5 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2025-02-10 DOI: 10.1016/j.chempr.2024.102407

Zhiyin Zhang, Huat T. Chiang, Ying Xia, Nicole Avakyan, Ravi R. Sonani, Fengbin Wang, Edward H. Egelman, James J. De Yoreo, Lilo D. Pozzo, F. Akif Tezcan

Host-guest (HG) interactions have been widely used to build responsive materials and molecular machines owing to their inherently dynamic nature, interaction specificity, and responsiveness to diverse stimuli. Here, we have set out to exploit these advantages of HG chemistry in the design of dynamic protein assemblies, using a C₄ symmetric protein, ^C98RhuA, as a building block. We show that a ^C98RhuA variant individually modified with β-cyclodextrin (βCD) (host) or azobenzene (guest) functionalities can specifically pair with each other to form highly ordered 1D and 2D assemblies. Association and dissociation of ^βCDRhuA-^azoRhuA assemblies can be controlled by UV and visible light as well as by small-molecule modulators of βCD-azobenzene interactions. Kinetics analyses reveal that ^βCDRhuA-^azoRhuA nanotubes assemble without a nucleation barrier, a highly unusual occurrence for helical supramolecular systems. Taken together, our findings provide a compelling example for achieving complex structural and dynamic outcomes in protein assembly through simple chemical design.

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