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Photocatalytic hydrogenation of alkenes using ammonia-borane 氨硼烷催化烯烃的光催化加氢

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102711

Eva Rivera-Chao , Wesley J. Olivier , Michael J. Tilby , Daniele Leonori

Alkene hydrogenation is one of the most widely used reactions for producing high-value materials. Traditional methods rely on H₂ gas under transition metal catalysis, which presents challenges related to cost, safety, waste management, and undesired reactivity. An ideal hydrogenation method would circumvent both components by employing a hydrogen storage material under mild, metal-free conditions. Herein, we introduce a photocatalytic strategy for alkene hydrogenation using H₃N-BH₃. Our system harnesses visible light with a diaryl ketone photocatalyst to convert H₃N-BH₃ into its corresponding boryl radical. This open-shell species undergoes a complex sequence of transformations, including a key halogen-atom transfer with the solvent, in situ generation of alkyl borane intermediates, H-atom transfer to generate an aminyl radical, and subsequent β-fragmentation to engage with a thiol co-catalyst. This H₂- and metal-free approach enables the transformation of a broad range of alkenes, tolerating functional groups typically incompatible with standard protocols.

烯烃加氢反应是生产高价值材料应用最广泛的反应之一。传统的方法依赖于过渡金属催化下的氢气，这带来了成本、安全性、废物管理和不良反应性等方面的挑战。理想的加氢方法是在温和的、无金属的条件下使用储氢材料来绕过这两种成分。本文介绍了一种用H3N-BH3光催化烯烃加氢的方法。我们的系统利用可见光和二芳基酮光催化剂将H3N-BH3转化为相应的硼基自由基。这种开壳物质经历了一系列复杂的转化，包括与溶剂的关键卤素原子转移，烷基硼烷中间体的原位生成，h原子转移生成氨基自由基，以及随后的β断裂与硫醇共催化剂结合。这种不含H2和金属的方法可以转化广泛的烯烃，容忍通常与标准协议不相容的官能团。

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引用次数: 0

Spatially resolved reaction environments in mechanochemical upcycling of polymers 聚合物机械化学升级循环中的空间分解反应环境

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102754

Kinga Gołąbek , Yuchen Chang , Lauren R. Mellinger , Mariana V. Rodrigues , Cauê de Souza Coutinho Nogueira , Fabio B. Passos , Yutao Xing , Aline Ribeiro Passos , Mohammed H. Saffarini , Austin B. Isner , David S. Sholl , Carsten Sievers

Mechanochemical processing is an attractive and scalable approach for the upcycling of polymers. The complex and dynamic environment in ball milling, however, makes gaining insight into the physicochemical nature of the collisions driving mechanochemistry challenging, which, in turn, hampers the optimization of these processes. We used controlled single impacts followed by multiple spatially resolved analytical methods (focused ion beam microscopy, Raman spectro-microscopy, and small-angle X-ray scattering) and material point method simulations to gain unprecedented information about mechanochemical depolymerization of poly(ethylene terephthalate). These measurements highlight the contributions of plastic deformation, amorphization, and depolymerization during the transfer of kinetic energy in collisions relevant to ball mills and will enable reactor models based on fundamental kinetics.

机械化学处理是一种有吸引力和可扩展的聚合物升级回收方法。然而，球磨过程中复杂的动态环境使得深入了解碰撞驱动机械化学的物理化学性质具有挑战性，这反过来又阻碍了这些过程的优化。我们采用受控的单次冲击，随后采用多种空间分辨分析方法（聚焦离子束显微镜、拉曼光谱显微镜和小角度x射线散射）和物质点法模拟，以获得有关聚对苯二甲酸乙酯机械化学解聚的前所未有的信息。这些测量强调了在与球磨机相关的碰撞中动能转移过程中的塑性变形、非晶化和解聚的贡献，并将使基于基本动力学的反应器模型成为可能。

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引用次数: 0

Photocatalytic overall reactions over MOFs and COFs mof和COFs的光催化全反应

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102778

Zhenwei Zhang , Yunyang Qian , Hai-Long Jiang

Solar energy is the most abundant energy source in nature, making photocatalysis a promising solution to global energy and environmental challenges. Because photocatalytic pathways are intrinsically complex, catalysts with precise, tunable structures are crucial for mechanism study. Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs)—crystalline, porous frameworks with customizable structures and large surface areas—have garnered significant attention in photocatalysis. However, most studies on MOFs and COFs have largely focused on half-reactions, relying on costly sacrificial agents and discarding photogenerated holes, which hinder the further development. Therefore, this review begins by highlighting the unique benefits of MOFs and COFs and the necessity of promoting photocatalytic overall reaction processes with them. We then outline strategies to enhance their performance—especially for overall reactions—and survey recent advances in water splitting, CO₂ reduction, H₂O₂ synthesis, dual-functional reactions, and methane oxidation. Finally, key challenges and future prospects for MOF- and COF-driven photocatalytic overall reactions are discussed.

太阳能是自然界中最丰富的能源，使光催化成为解决全球能源和环境挑战的有希望的解决方案。由于光催化途径本质上是复杂的，具有精确、可调结构的催化剂对于机理研究至关重要。金属有机框架（MOFs）和共价有机框架（COFs）是具有可定制结构和大表面积的晶体多孔框架，在光催化领域引起了广泛的关注。然而，大多数关于mof和COFs的研究主要集中在半反应上，依赖于昂贵的牺牲剂和丢弃光生孔，这阻碍了进一步的发展。因此，本文首先介绍了mof和COFs的独特优势，以及它们促进光催化全反应过程的必要性。然后，我们概述了提高其性能的策略，特别是对于整体反应，并概述了在水分解、CO2还原、H2O2合成、双功能反应和甲烷氧化方面的最新进展。最后，讨论了MOF和cof驱动光催化全反应的主要挑战和未来前景。

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引用次数: 0

Fast reverse intersystem crossing over 107 s−1 via near-enantiomeric charge-transfer transitions 通过近对映体电荷转移跃迁，在107 s−1内快速反向系统间交叉

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102685

Hai Zhang , Tianyu Huang , Jianping Zhou , Chunlin Xu , Dongdong Zhang , Lian Duan

Thermally activated delayed fluorescence (TADF) enables high-efficiency organic light-emitting diodes (OLEDs) through reverse intersystem crossing (RISC) of triplet excitons, yet existing systems struggle to achieve fast RISC rates (k_RISC >10⁷ s⁻¹), let alone balance a high radiative decay (k_r). Herein, we develop a dual-donor TADF emitter that bypasses the El-Sayed rule restriction by harnessing near-enantiomeric charge-transfer transitions between a high-lying triplet state and the lowest singlet state and that synergizes with heavy atoms to enhance spin-orbit coupling. This design yields a k_RISC of 1.54 × 10⁷ s⁻¹ alongside a k_r of 9.65 × 10⁶ s⁻¹, reducing the delayed fluorescence lifetime to 1.46 μs. The OLED exhibits a peak external quantum efficiency of 30.6% with minimal roll-off (30.4% at 5,000 cd m⁻²) and an operational lifetime exceeding 1,500 h at 1,000 cd m⁻² before the luminance decays to 95% of its initial value, which extends further to 3,876 h via sensitized narrowband emission. This work bypasses conventional localized triplet-intermediate-dependent RISC mechanisms and establishes a paradigm for designing high-efficiency, stable TADF materials.

热激活延迟荧光（TADF）通过三重态激子的反向系统间交叉（RISC）实现高效有机发光二极管（oled），但现有系统难以实现快速的RISC速率（kRISC >107 s−1），更不用说平衡高辐射衰减（kr）了。在此，我们开发了一种双供体TADF发射极，通过利用高三重态和最低单重态之间的近对构象电荷转移跃迁来绕过El-Sayed规则限制，并与重原子协同增强自旋轨道耦合。该设计产生的kRISC为1.54 × 107 s−1，kr为9.65 × 106 s−1，将延迟荧光寿命降低到1.46 μs。OLED的最大外量子效率为30.6%，滚降最小（在5,000 cd m−2时为30.4%），在1,000 cd m−2时的工作寿命超过1,500 h，然后亮度衰减到其初始值的95%，通过敏化窄带发射进一步延长至3,876 h。这项工作绕过了传统的局部三重中间体依赖的RISC机制，为设计高效、稳定的TADF材料建立了一个范例。

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引用次数: 0

A catalytic approach to the valorization of polyesters and biogenic waste for the production of amines 聚酯和生物废物催化增值生产胺的方法

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102667

Fairoosa Poovan , Rajenahally V. Jagadeesh , Matthias Beller

Despite the numerous applications of polymers in human life, their excessive use has caused serious environmental hazards. Among polymer recycling methods, chemical recycling offers a streamlined approach to polymer degradation by enabling depolymerization without compromising functionality. Specifically, hydrogenolysis of polymers, a depolymerization technique that utilizes hydrogen to cleave bonds, has emerged as a powerful strategy for depolymerization, facilitating the upcycling of plastics into high-value chemicals. Previous research in this area has predominantly focused on noble metal catalysts, while the potential of base metals remains unexplored. Herein, we propose a cobalt-based hydrogenative amination approach for the depolymerization of polyesters to versatile diamines as well as amino alcohols. This strategy can also be applied to the one-pot synthesis of fatty amines from used cooking oil. The current system opens new avenues for the upcycling of waste into valuable amines, providing a viable solution to plastic pollution and a way to utilize waste as a resource.

尽管聚合物在人类生活中有着广泛的应用，但其过度使用已经造成了严重的环境危害。在聚合物回收方法中，化学回收提供了一种简化的方法，通过使解聚不影响功能来降解聚合物。具体来说，聚合物的氢解是一种利用氢裂解键的解聚技术，已经成为解聚的一种强大策略，促进了塑料升级回收成为高价值化学品。该领域以前的研究主要集中在贵金属催化剂上，而贱金属催化剂的潜力尚未开发。在这里，我们提出了一种基于钴的氢化胺化方法，用于聚酯解聚到通用二胺和氨基醇。该方法也适用于用废食用油一锅法合成脂肪胺。目前的系统为将废物升级为有价值的胺开辟了新的途径，为塑料污染提供了可行的解决方案，并为利用废物作为资源提供了一种方法。

引用次数: 0

Energy conversion and loss in heterojunction photocatalysts 异质结光催化剂的能量转换和损失

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102719

Liuyang Zhang , Jianjun Zhang , Jiaguo Yu

Photocatalysis has gained significant attention due to its wide range of potential applications. Recent studies highlight impressive energy conversion efficiency and quantum yield. This perspective aims to facilitate a better comprehension of the photocatalytic processes through analysis. Traditionally viewed as the direct conversion of light energy to chemical energy, photocatalytic processes are now understood to involve light undergoing a two-step conversion: first to electrical energy and then to chemical energy. Three major factors contribute to energy losses. Firstly, external factors include absorption, reflection, and scattering of light on the reactor surface as well as light absorption by the solution and partial light transmission across the reactor. Secondly, internal factors encompass the energy loss derived from vibrational relaxation and the disappearance of the photogenerated charge carriers. Lastly, reverse reactions induce product decomposition. In summary, achieving 100% energy conversion efficiency and quantum yield is extremely challenging and nearly impossible considering these various factors.

光催化因其广泛的应用前景而受到广泛关注。最近的研究强调了令人印象深刻的能量转换效率和量子产率。这一观点旨在通过分析促进对光催化过程的更好理解。传统上认为光催化过程是光能直接转化为化学能，而现在人们认为光催化过程是光经历两步转化：首先转化为电能，然后转化为化学能。造成能量损失的主要因素有三个。首先，外部因素包括光在反应器表面的吸收、反射和散射，以及溶液对光的吸收和部分光通过反应器的透射。其次，内部因素包括由振动松弛引起的能量损失和光生载流子的消失。最后，逆反应诱导产物分解。总之，考虑到这些不同的因素，实现100%的能量转换效率和量子产率是极具挑战性的，几乎是不可能的。

引用次数: 0

Modular synthesis of fluoroalkyl-substituted cyclopropenes with fluoroalkylacylsilanes as carbynyl cation equivalents 氟烷基取代环丙烯与氟烷基丙烯基硅烷作为羰基阳离子等价物的模块化合成

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102721

Gang Zhou , Yuan Yao , Xiaoqian He , Weilu Zhang , Shanshan Liu , Xiao Shen

The carbynyl cation, which is a reactive species capable of forming three covalent bonds, remains relatively unexplored due to its extreme reactivity and the limited availability of efficient sources. Herein, we report the application of fluoroalkylacylsilanes as carbynyl cation equivalents, enabling the modular synthesis of fluoroalkyl-substituted cyclopropenes, where three new covalent bonds are constructed. The success of this reaction lies in the integration of sequential photocatalysis and acid catalysis in a one-pot process. Photocatalysis facilitates the carbene-mediated [2 + 1] cycloaddition with alkynes, while acid catalysis promotes formal C–O bond functionalization via cyclopropenium intermediates. Using this strategy, we have synthesized a diverse array of fluoroalkylated cyclopropenyl ethers, arenes, alkanes, thioethers, amines, and azides. These reactions are not only effective for the synthesis of simple cyclopropenes but also provide access to complex cyclopropenes that are otherwise challenging to prepare.

羰基阳离子是一种能够形成三个共价键的反应性物质，由于其极强的反应性和有效来源的有限性，仍然相对未被开发。本文中，我们报道了氟烷基烷基硅烷作为羰基阳离子等价物的应用，使得氟烷基取代环丙烯的模块化合成成为可能，其中构建了三个新的共价键。该反应的成功之处在于将顺序光催化和酸催化在一锅过程中结合起来。光催化促进了碳介导的[2 + 1]与炔烃的环加成反应，而酸催化通过环丙烯中间体促进了正式的C-O键功能化。使用这种策略，我们已经合成了各种氟烷基化环丙烯醚、芳烃、烷烃、硫醚、胺和叠氮化物。这些反应不仅对简单环丙烯的合成有效，而且还提供了制备复杂环丙烯的途径，否则很难制备。

引用次数: 0

Radical sorting as a general framework for deaminative C(sp3)–C(sp2) cross-coupling 自由基分选作为脱胺C(sp3) -C （sp2）交叉耦合的一般框架

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102716

Deepta Chattapadhyay , En-Chih Liu , Mark Jeffrey Diaz , Arunava Maity , Benjamin A. Bratten , Quentin Michaudel

Radical-based transition-metal-catalyzed cross-couplings are invaluable tools in synthetic medicinal chemistry. Although carboxylic acids are now routinely used as radical precursors, aliphatic primary amines—an equally abundant class of building blocks—are less commonly used in radical coupling. We present a general method for deaminative cross-coupling relying on a dual-catalytic system that generates geminate pairs of non-identical alkyl radicals via photosensitization of unsymmetrical 1,2-dialkyldiazenes, then selectively engages the desired radical species in C(sp³)–C(sp²) bond formation. This Ni-mediated “radical sorting” of geminate radical pairs is key in obtaining high yields and avoiding side products. This approach capitalizes on the versatility of the sulfur(VI) fluoride exchange (SuFEx) click reaction combined with the aza-Ramberg-Bäcklund reaction and enables the functionalization of a broad array of structurally diverse primary amines—including peptide derivatives and synthetic pharmaceutical intermediates. Mechanistic insights from this work open unique avenues for radical-based cross-couplings.

基于自由基的过渡金属催化的交叉偶联是合成药物化学的宝贵工具。虽然羧酸现在通常被用作自由基前体，但脂肪族伯胺——同样丰富的一类构建块——在自由基偶联中较少使用。我们提出了一种通用的脱胺交叉偶联方法，该方法依赖于双催化系统，该系统通过不对称的1,2-二烷基二氮的光敏作用产生不相同的双共轭烷基自由基对，然后选择性地在C(sp3) -C （sp2）键形成中接合所需的自由基。这种镍介导的双自由基对的“自由基分选”是获得高收率和避免副作用的关键。这种方法利用硫（VI）氟交换（SuFEx）点击反应的多功能性与aza-Ramberg-Bäcklund反应相结合，使多种结构多样的伯胺（包括肽衍生物和合成药物中间体）的功能化成为可能。这项工作的机械见解为基于激进的交叉耦合开辟了独特的途径。

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引用次数: 0

Pillar-cage fluorinated hybrid porous frameworks featuring quasi-Johnson solid J28 具有准约翰逊固体J28的柱笼式氟化混合多孔框架

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102696

Cheng Chen , Shuixiang Zou , Daqiang Yuan , Mingyan Wu

Adsorptive separation process based on porous materials is widely employed in various separation scenarios owing to its mild operating conditions and energy-efficient characteristics. In this study, we present a bottom-up, self-assembly approach to synthesize a novel pillar-cage fluorinated hybrid porous framework (TIFSIX-Cu-J), which exhibits a rare crystalline quasi-Johnson solid J₂₈ structure. Notably, this material undergoes heat-triggered structural transformation, resulting in a new distorted square orthobicupola structure (TIFSIX-Cu-J1). The structural changes were elucidated through detailed analysis of the single-crystal-to-single-crystal transformation and bulk crystalline powder X-ray diffraction. The resulting framework demonstrates significantly enhanced performance in separating trace propyne from propylene. In situ breakthrough experiments show that the TIFSIX-Cu-J1-packed column can achieve approximately 20-fold higher C₃H₆ productivity (≥99.95%) compared with TIFSIX-Cu-J at 298 K and 1 bar. This study presents the first successful fabrication of crystalline square orthobicupola frameworks demonstrating in situ structural transformation characteristics, which exhibit significant potential for energy-efficient gas purification applications.

基于多孔材料的吸附分离工艺以其操作条件温和、节能等特点被广泛应用于各种分离场合。在这项研究中，我们提出了一种自下而上的自组装方法来合成一种新型柱笼型氟化杂化多孔框架（tif6 - cu - j），该框架具有罕见的晶体准约翰逊固体J28结构。值得注意的是，这种材料经历了热触发的结构转变，产生了一种新的扭曲的方形正二元体结构（tif6 - cu - j1）。通过单晶向单晶转变和体晶粉末x射线衍射的详细分析，阐明了结构变化。结果表明，该框架在分离微量丙烯和丙烯方面的性能显著提高。原位突破实验表明，在298 K和1 bar条件下，tif6 - cu - j1填充柱的C3H6产率比tif6 - cu - j高出约20倍（≥99.95%）。本研究首次成功制备了方形正畸体晶体框架，展示了原位结构转化特性，在节能气体净化应用中表现出巨大的潜力。

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引用次数: 0

An aqueous artificial molecular pump 一种水人工分子泵

IF 19.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chem

Pub Date : 2026-01-15 DOI: 10.1016/j.chempr.2025.102693

Christopher K. Lee , Yuanning Feng , Alan E. Enciso , Jake P. Violi , William A. Donald , J. Fraser Stoddart , Dong Jun Kim

This work presents an artificial molecular pump designed for efficient operation in water, advancing the integration of synthetic molecular machines into biologically relevant environments. The pump function, demonstrated through the formation of [2]- and [3]rotaxanes, exhibits enhanced efficiency and faster kinetics compared with analogous systems in organic solvents. These improvements stem from radical-radical interactions amplified by water due to its high polarity, emphasizing the solvent’s role in molecular machine performance. The findings underscore the ability of water to strengthen supramolecular interactions essential for pump operation, providing a framework for designing next-generation molecular machines capable of functioning under more biochemically relevant conditions.

这项工作提出了一种人工分子泵，旨在有效地在水中运行，推进合成分子机器与生物相关环境的整合。泵浦功能，通过[2]-和[3]轮烷的形成证明，与有机溶剂中的类似系统相比，具有更高的效率和更快的动力学。这些改进源于自由基与自由基的相互作用，由于水的高极性而被放大，强调了溶剂在分子机器性能中的作用。这些发现强调了水加强超分子相互作用的能力，这对泵的运行至关重要，为设计能够在更多生化相关条件下运行的下一代分子机器提供了框架。

引用次数: 0

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