Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.06.029
Yi Tao , Cuihua Jin , Chuanwang Liu , Jiawei Bu , Ling Yue , Xipan Li , Kangjiang Liang , Chengfeng Xia
Deuterium incorporation into pharmaceutical molecules has been recognized as having a positive impact on drug efficacy and safety, allowing improvements in pharmacokinetic and/or toxicity profiles. Due to the high chemical inertness of arenes toward the hydrogen atom and the electron transfer processes, the visible light-induced direct deuteration of aromatic C(sp2)–H bonds via hydrogen isotope exchange remains unexplored. Herein, we report a photochemical deuteration protocol for efficient incorporation of deuterium into arenes in a single step, tolerating manifold functionalities in pharmaceutical compounds. Mechanistic studies provided evidence that solvated electrons were generated by light illumination with a phenolate-type photocatalyst and were involved in deuterium incorporation. This protocol was successfully applied to the late-stage deuteration of pharmaceuticals by photochemical aromatic H/D exchange on arenes.
{"title":"Deuteration of arenes in pharmaceuticals via photoinduced solvated electrons","authors":"Yi Tao , Cuihua Jin , Chuanwang Liu , Jiawei Bu , Ling Yue , Xipan Li , Kangjiang Liang , Chengfeng Xia","doi":"10.1016/j.chempr.2024.06.029","DOIUrl":"10.1016/j.chempr.2024.06.029","url":null,"abstract":"<div><div><span>Deuterium<span><span> incorporation into pharmaceutical molecules has been recognized as having a positive impact on drug efficacy and safety, allowing improvements in pharmacokinetic and/or toxicity profiles. Due to the high chemical inertness of arenes toward the </span>hydrogen atom<span> and the electron transfer processes, the visible light-induced direct deuteration of aromatic C(sp</span></span></span><sup>2</sup><span><span>)–H bonds via hydrogen isotope<span> exchange remains unexplored. Herein, we report a photochemical deuteration protocol for efficient incorporation of deuterium into arenes in a single step, tolerating manifold functionalities in pharmaceutical compounds. Mechanistic studies provided evidence that </span></span>solvated electrons were generated by light illumination with a phenolate-type photocatalyst and were involved in deuterium incorporation. This protocol was successfully applied to the late-stage deuteration of pharmaceuticals by photochemical aromatic H/D exchange on arenes.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3374-3384"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141726489","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.06.034
Sebastian M. Kopp , Henrik Gotfredsen , Janko Hergenhahn , Arnau Rodríguez-Rubio , Jie-Ren Deng , He Zhu , Wojciech Stawski , Harry L. Anderson
Aromatic and antiaromatic ring currents can reveal global electronic delocalization around the circumference of π-conjugated macrocycles, although these phenomena are poorly understood in large rings. Here, we present the template-directed synthesis of a fully π-conjugated cyclic porphyrin 12-mer consisting of six β,meso,β-edge-fused porphyrin dimers connected by six butadiyne bridges. The lowest energy π-π∗ absorption band of this partially fused nanoring is shifted far into the NIR, confirming strong π-conjugation around the circumference of the macrocycle. Investigation of the oxidized and reduced nanoring-template complex by 1H and 19F NMR spectroscopy demonstrates the presence of coherent global (anti)aromatic ring currents, consistent with DFT calculations. The stronger π-conjugation enables global charge delocalization even at low levels of oxidation or reduction. These findings open new avenues for the engineering of cyclic molecular wires.
{"title":"Charge delocalization and global aromaticity in a partially fused 12-porphyrin nanoring","authors":"Sebastian M. Kopp , Henrik Gotfredsen , Janko Hergenhahn , Arnau Rodríguez-Rubio , Jie-Ren Deng , He Zhu , Wojciech Stawski , Harry L. Anderson","doi":"10.1016/j.chempr.2024.06.034","DOIUrl":"10.1016/j.chempr.2024.06.034","url":null,"abstract":"<div><div>Aromatic and antiaromatic ring currents can reveal global electronic delocalization around the circumference of <em>π</em>-conjugated macrocycles, although these phenomena are poorly understood in large rings. Here, we present the template-directed synthesis of a fully <em>π</em>-conjugated cyclic porphyrin 12-mer consisting of six <em>β</em>,<em>meso</em>,<em>β</em>-edge-fused porphyrin dimers connected by six butadiyne bridges. The lowest energy <em>π</em>-<em>π</em>∗ absorption band of this partially fused nanoring is shifted far into the NIR, confirming strong <em>π</em>-conjugation around the circumference of the macrocycle. Investigation of the oxidized and reduced nanoring-template complex by <sup>1</sup>H and <sup>19</sup>F NMR spectroscopy demonstrates the presence of coherent global (anti)aromatic ring currents, consistent with DFT calculations. The stronger <em>π</em>-conjugation enables global charge delocalization even at low levels of oxidation or reduction. These findings open new avenues for the engineering of cyclic molecular wires.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3410-3427"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754427","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.09.025
Mihrimah Ozkan, Saeb Besarati, Christopher Gordon, Gaël Gobaille-Shaw, Noah McQueen
Advancements in cost-effective direct air capture (DAC) technology have become critical in addressing climate change, with a particular emphasis on energy and cost reductions. Recent innovations have significantly decreased the energy requirements of DAC systems. In collaboration with experts from industry leaders such as Climeworks, Carbon Capture, Mission Zero, and Heirloom, the latest developments highlight DAC technology’s potential to become a viable and sustainable solution for large-scale CO₂ removal. These advancements include reductions in energy consumption to as low as 1,055 kWh per ton of CO₂ through electrochemical methods and strategic integration of renewable energy sources like geothermal power. Additionally, economies of scale achieved through bulk purchasing and streamlined manufacturing processes have lowered DAC modules’ per-unit cost. Financial incentives and supportive policies, such as the 45Q tax credit in the United States, enhance the economic feasibility of these technologies. These innovations underscore the substantial contributions of DAC technology to global climate change mitigation efforts, making it a promising solution for achieving significant reductions in atmospheric CO₂ levels.
{"title":"Advancements in cost-effective direct air capture technology","authors":"Mihrimah Ozkan, Saeb Besarati, Christopher Gordon, Gaël Gobaille-Shaw, Noah McQueen","doi":"10.1016/j.chempr.2024.09.025","DOIUrl":"10.1016/j.chempr.2024.09.025","url":null,"abstract":"<div><div>Advancements in cost-effective direct air capture (DAC) technology have become critical in addressing climate change, with a particular emphasis on energy and cost reductions. Recent innovations have significantly decreased the energy requirements of DAC systems. In collaboration with experts from industry leaders such as Climeworks, Carbon Capture, Mission Zero, and Heirloom, the latest developments highlight DAC technology’s potential to become a viable and sustainable solution for large-scale CO₂ removal. These advancements include reductions in energy consumption to as low as 1,055 kWh per ton of CO₂ through electrochemical methods and strategic integration of renewable energy sources like geothermal power. Additionally, economies of scale achieved through bulk purchasing and streamlined manufacturing processes have lowered DAC modules’ per-unit cost. Financial incentives and supportive policies, such as the 45Q tax credit in the United States, enhance the economic feasibility of these technologies. These innovations underscore the substantial contributions of DAC technology to global climate change mitigation efforts, making it a promising solution for achieving significant reductions in atmospheric CO₂ levels.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3261-3265"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142662853","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.07.001
Mihai V. Popescu , Robert S. Paton
A computational approach for modeling and predicting triplet energy sensitization of organic molecules is described, which involves sampling the instantaneous, vertical energy gaps over molecular vibrational motions. This approach provides new theoretical support for the hot-band mechanism of energy transfer, in which the energy difference between donor and acceptor can be lessened by geometric distortions. We demonstrate excellent predictive performance against experimental triplet energies, with R2 = 0.97 and a mean absolute error (MAE) of 1.7 kcal/mol, for a collection of 24 small organic molecules, whereas a static, adiabatic description performs significantly worse (R2 = 0.51, MAE = 9.5 kcal/mol). Using this approach, it is possible to quantitatively predict the correct E/Z-isomerism of alkenes under energy transfer, for which adiabatic calculations predict the wrong outcome.
{"title":"Dynamic vertical triplet energies: Understanding and predicting triplet energy transfer","authors":"Mihai V. Popescu , Robert S. Paton","doi":"10.1016/j.chempr.2024.07.001","DOIUrl":"10.1016/j.chempr.2024.07.001","url":null,"abstract":"<div><div>A computational approach for modeling and predicting triplet energy sensitization of organic molecules is described, which involves sampling the instantaneous, vertical energy gaps over molecular vibrational motions. This approach provides new theoretical support for the hot-band mechanism of energy transfer, in which the energy difference between donor and acceptor can be lessened by geometric distortions. We demonstrate excellent predictive performance against experimental triplet energies, with R<sup>2</sup> = 0.97 and a mean absolute error (MAE) of 1.7 kcal/mol, for a collection of 24 small organic molecules, whereas a static, adiabatic description performs significantly worse (R<sup>2</sup> = 0.51, MAE = 9.5 kcal/mol). Using this approach, it is possible to quantitatively predict the correct <em>E</em>/<em>Z-</em>isomerism of alkenes under energy transfer, for which adiabatic calculations predict the wrong outcome.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3428-3443"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141764546","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}
Pub Date : 2024-11-13DOI: 10.1016/j.chempr.2024.10.016
Till L. Kalkuhl, Israel Fernández, Terrance J. Hadlington
The discovery of unique mechanisms in 3d metal catalysis is of paramount importance in utilizing these Earth-abundant metals in place of scarce precious metals. Inspired by the Horiuti-Polanyi mechanism at play in heterogeneous hydrogenation catalysts, we describe a bimetallic molecular catalyst that can selectively semi-hydrogenate alkynes via a ligand-to-substrate hydride transfer mechanism. This mimics established heterogeneous mechanisms in which remote surface-bound hydride ligands undergo a similar reactive process. This is achieved through the development of a chelate-constrained gallium(I) ligand, which operates in concert with nickel(0) to (reversibly) cleave H2, generating a [GaNi] 1,2-dihydride complex that is found to be the resting state in the catalytic process. This discovery takes steps toward utilizing non-innocent low-valent group 13 centers in effective cooperative catalysis, opening new mechanistic pathways that may aid in employing Earth-abundant metals in key catalytic transformations.
发现 3d 金属催化的独特机制对于利用这些地球上丰富的金属来替代稀缺的贵金属至关重要。受异相氢化催化剂中 Horiuti-Polanyi 机制的启发，我们描述了一种双金属分子催化剂，它可以通过配体到底物的氢化物转移机制选择性地半氢化炔烃。这模仿了已建立的异质机制，其中远距离表面结合的氢化物配体也经历了类似的反应过程。这是通过开发一种受螯合物约束的镓（I）配体实现的，该配体与镍（0）协同（可逆地）裂解 H2，生成[GaNi] 1,2-二酸酐复合物，该复合物被发现是催化过程中的静止状态。这一发现为利用非无辜的低价 13 族中心进行有效的合作催化迈出了一步，开辟了新的机理途径，可能有助于在关键的催化转化过程中使用地球上富集的金属。
{"title":"Cooperative hydrogenation catalysis at a constrained gallylene-nickel(0) interface","authors":"Till L. Kalkuhl, Israel Fernández, Terrance J. Hadlington","doi":"10.1016/j.chempr.2024.10.016","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.016","url":null,"abstract":"The discovery of unique mechanisms in 3<em>d</em> metal catalysis is of paramount importance in utilizing these Earth-abundant metals in place of scarce precious metals. Inspired by the Horiuti-Polanyi mechanism at play in heterogeneous hydrogenation catalysts, we describe a bimetallic molecular catalyst that can selectively semi-hydrogenate alkynes via a ligand-to-substrate hydride transfer mechanism. This mimics established heterogeneous mechanisms in which remote surface-bound hydride ligands undergo a similar reactive process. This is achieved through the development of a chelate-constrained gallium(I) ligand, which operates in concert with nickel(0) to (reversibly) cleave H<sub>2</sub>, generating a [GaNi] 1,2-dihydride complex that is found to be the resting state in the catalytic process. This discovery takes steps toward utilizing non-innocent low-valent group 13 centers in effective cooperative catalysis, opening new mechanistic pathways that may aid in employing Earth-abundant metals in key catalytic transformations.","PeriodicalId":268,"journal":{"name":"Chem","volume":"163 11 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601923","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}
Pub Date : 2024-11-12DOI: 10.1016/j.chempr.2024.10.013
Julie Yi-Hsuan Chen, Qing Shi, Xue Peng, Jean de Dieu Habimana, James Wang, William Sobolewski, Andy Hsien-Wei Yeh
We leverage AI-powered de novo protein design to create a new generation of luciferase catalysts, termed the neoLux series, which exhibit superior properties over native luciferases. These features include compact size, robust stability, cofactor independence, efficient cellular expression, higher catalytic efficiency, and unique substrate orthogonality, marking a significant advancement beyond the limitations of native luciferases. Additionally, we computationally designed highly efficient neoLux-fluorescent protein Förster resonance energy transfer (FRET) fusions capable of simultaneous multi-parametric imaging in cellulo and in vivo. Our pioneering approach has created a unified luminescent toolkit to allow for multi-colored tracking of cancer heterogeneity in vivo, paving the way for complex biological discovery.
{"title":"De novo luciferases enable multiplexed bioluminescence imaging","authors":"Julie Yi-Hsuan Chen, Qing Shi, Xue Peng, Jean de Dieu Habimana, James Wang, William Sobolewski, Andy Hsien-Wei Yeh","doi":"10.1016/j.chempr.2024.10.013","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.013","url":null,"abstract":"We leverage AI-powered <em>de novo</em> protein design to create a new generation of luciferase catalysts, termed the neoLux series, which exhibit superior properties over native luciferases. These features include compact size, robust stability, cofactor independence, efficient cellular expression, higher catalytic efficiency, and unique substrate orthogonality, marking a significant advancement beyond the limitations of native luciferases. Additionally, we computationally designed highly efficient neoLux-fluorescent protein Förster resonance energy transfer (FRET) fusions capable of simultaneous multi-parametric imaging <em>in cellulo</em> and <em>in vivo</em>. Our pioneering approach has created a unified luminescent toolkit to allow for multi-colored tracking of cancer heterogeneity <em>in vivo</em>, paving the way for complex biological discovery.","PeriodicalId":268,"journal":{"name":"Chem","volume":"72 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599734","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}
Pub Date : 2024-11-06DOI: 10.1016/j.chempr.2024.10.007
Wanying Han, Longfei Lin, Ziyu Cen, Yubin Ke, Qian Xu, Junfa Zhu, Xuelei Mei, Zhanghui Xia, Xinrui Zheng, Yaqin Wang, Yani Liu, Mingyuan He, Haihong Wu, Buxing Han
Chemical upcycling of polyethylene (PE) waste presents a viable and promising approach to address the issues of plastic waste accumulation. However, developing cost-effective and efficient routes for converting PE waste into value-added products remains a challenging task. Here, we report a one-pot, dual-catalyst system for efficient conversion of PE into gasoline without the need for noble-metal catalysts, external hydrogen, or solvents. A gasoline yield of up to 87% is achieved over a dual-catalyst system comprising WZr-KIT-6 and HZSM-5 at 240°C. The WZr-KIT-6 catalyst facilitated the activation and pre-cracking of PE chains into unsaturated oligomers over Si-O-Zr and W-O(H)-Zr sites. These unsaturated oligomers, characterized by increased mobility and reactivity, were subsequently converted into C4–C12 gasoline-range compounds through β-scission, isomerization, and hydride transfer over HZSM-5. The synergistic reaction mechanism over mesoporous and microporous materials was crucial for enhancing the efficiency and selectivity of PE conversion.
{"title":"One-pot catalytic conversion of polyethylene wastes to gasoline through a dual-catalyst system","authors":"Wanying Han, Longfei Lin, Ziyu Cen, Yubin Ke, Qian Xu, Junfa Zhu, Xuelei Mei, Zhanghui Xia, Xinrui Zheng, Yaqin Wang, Yani Liu, Mingyuan He, Haihong Wu, Buxing Han","doi":"10.1016/j.chempr.2024.10.007","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.007","url":null,"abstract":"Chemical upcycling of polyethylene (PE) waste presents a viable and promising approach to address the issues of plastic waste accumulation. However, developing cost-effective and efficient routes for converting PE waste into value-added products remains a challenging task. Here, we report a one-pot, dual-catalyst system for efficient conversion of PE into gasoline without the need for noble-metal catalysts, external hydrogen, or solvents. A gasoline yield of up to 87% is achieved over a dual-catalyst system comprising WZr-KIT-6 and HZSM-5 at 240°C. The WZr-KIT-6 catalyst facilitated the activation and pre-cracking of PE chains into unsaturated oligomers over Si-O-Zr and W-O(H)-Zr sites. These unsaturated oligomers, characterized by increased mobility and reactivity, were subsequently converted into C<sub>4</sub>–C<sub>12</sub> gasoline-range compounds through β-scission, isomerization, and hydride transfer over HZSM-5. The synergistic reaction mechanism over mesoporous and microporous materials was crucial for enhancing the efficiency and selectivity of PE conversion.","PeriodicalId":268,"journal":{"name":"Chem","volume":"31 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589051","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}
Pub Date : 2024-11-04DOI: 10.1016/j.chempr.2024.10.008
Linh Duy Thai, Jochen A. Kammerer, Dmitri Golberg, Hatice Mutlu, Christopher Barner-Kowollik
The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.
{"title":"Sequence-defined main-chain photoswitching macromolecules with odd-even effect-controlled properties","authors":"Linh Duy Thai, Jochen A. Kammerer, Dmitri Golberg, Hatice Mutlu, Christopher Barner-Kowollik","doi":"10.1016/j.chempr.2024.10.008","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.008","url":null,"abstract":"The installation of stimuli-responsive moieties into their main chain maximizes the stimuli response of polymers. Yet, facile and orthogonal synthesis of such complex macromolecules is a daunting challenge, especially for achieving absolute chain-end-group fidelity, monodispersity, and the formation of block copolymers (BCPs). We harness metal-free hydroxyl-yne click and deprotection chemistry to realize monodisperse, sequence-defined oligomers and BCPs featuring α-bisimines as main-chain photoswitches and orthogonally incorporate functional terminal groups (olefins, acrylates, and non-activated alkynes). We reveal the significant influence of the sequence on solution and solid-state material properties, which manifests as a strong odd-even effect on the hydrodynamic volume, glass transition temperature, and BCP domain spacing. The odd-even effect originates from the distinct symmetries of the sequences resulting from our precise synthetic strategy. Thus, our sequence-defined, orthogonal synthesis strategy with near absolute chain-end-group fidelity and wide functional group compatibility paves the way toward complex polymeric materials with precise properties, topology, composition, and main-chain functionalities.","PeriodicalId":268,"journal":{"name":"Chem","volume":"126 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574648","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}
Pub Date : 2024-11-01DOI: 10.1016/j.chempr.2024.10.004
Jingzhen Du, Benjamin E. Atkinson, John A. Seed, Rebecca F. Sheppard, Floriana Tuna, Ashley J. Wooles, Nicholas F. Chilton, Stephen T. Liddle
The dominant form of elemental nitrogen on Earth is dinitrogen, but elemental phosphorus is found predominantly as white phosphorus or other singly bonded allotropes. Thus, there is interest in studying diphosphorus derivatives, most notably trapping between metal ions affording diphosphorus in +2, +1⋅, 0, 1−⋅, 2−, and 4− charge states. However, the diphosphorus radical trianion form had previously remained elusive due to the instability of main-group diatomics with large, odd negative charges. Here, we disclose a crystalline diuranium diphosphorus radical trianion complex with strong antiferromagnetic uranium-phosphorus magnetic exchange coupling parameters of up to −731 cm−1. This value is over five times greater than that of lanthanide analogues and is comparable to or exceeds d-block metal-metal and metal-ligand exchange couplings, despite being based on a 5f metal, which is typically regarded as possessing contracted valence orbitals compared with d-block ions. This highlights exchange-coupled f-element-p-block radical bridged character that can be engendered in molecular magnetism.
{"title":"Strong uranium-phosphorus antiferromagnetic exchange coupling in a crystalline diphosphorus radical trianion actinide complex","authors":"Jingzhen Du, Benjamin E. Atkinson, John A. Seed, Rebecca F. Sheppard, Floriana Tuna, Ashley J. Wooles, Nicholas F. Chilton, Stephen T. Liddle","doi":"10.1016/j.chempr.2024.10.004","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.004","url":null,"abstract":"The dominant form of elemental nitrogen on Earth is dinitrogen, but elemental phosphorus is found predominantly as white phosphorus or other singly bonded allotropes. Thus, there is interest in studying diphosphorus derivatives, most notably trapping between metal ions affording diphosphorus in +2, +1⋅, 0, 1−⋅, 2−, and 4− charge states. However, the diphosphorus radical trianion form had previously remained elusive due to the instability of main-group diatomics with large, odd negative charges. Here, we disclose a crystalline diuranium diphosphorus radical trianion complex with strong antiferromagnetic uranium-phosphorus magnetic exchange coupling parameters of up to −731 cm<sup>−1</sup>. This value is over five times greater than that of lanthanide analogues and is comparable to or exceeds d-block metal-metal and metal-ligand exchange couplings, despite being based on a 5f metal, which is typically regarded as possessing contracted valence orbitals compared with d-block ions. This highlights exchange-coupled f-element-p-block radical bridged character that can be engendered in molecular magnetism.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562033","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}
Pub Date : 2024-11-01DOI: 10.1016/j.chempr.2024.10.006
Xiao-Jing Xie, Heng Zeng, Yong-Liang Huang, Ying Wang, Qi-Yun Cao, Weigang Lu, Dan Li
Metal-organic frameworks (MOFs) with precisely controlled pore dimensions have greatly enriched the versatility of molecular sieving materials. Here, we report a channel-pore interconnected MOF (JNU-2) for direct production of o-xylene from six-component BTEXs (benzene, toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene) in a single adsorption process. Individual adsorption measurements show complete exclusion of o-xylene and benchmark adsorption of other BTEXs. Competitive adsorption studies reveal record-high adsorption selectivity of other BTEXs over o-xylene. Vapor-phase breakthrough experiments verify its superior separation potential for sieving o-xylene from BTEXs. We further demonstrate o-xylene purification by simply soaking JNU-2 (10 g) in BTEXs (18 mL, 90% o-xylene) at room temperature, realizing an average of 15.2 mL of o-xylene (99.5%+ purity, 94% recovery) for 10 cycles. Considering its exceptional stability, JNU-2 may have great promise for energy-efficient o-xylene separation from BTEXs.
{"title":"Direct production of o-xylene from six-component BTEXs using a channel-pore interconnected metal-organic framework","authors":"Xiao-Jing Xie, Heng Zeng, Yong-Liang Huang, Ying Wang, Qi-Yun Cao, Weigang Lu, Dan Li","doi":"10.1016/j.chempr.2024.10.006","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.006","url":null,"abstract":"Metal-organic frameworks (MOFs) with precisely controlled pore dimensions have greatly enriched the versatility of molecular sieving materials. Here, we report a channel-pore interconnected MOF (JNU-2) for direct production of <em>o</em>-xylene from six-component BTEXs (benzene, toluene, ethylbenzene, <em>o</em>-xylene, <em>m</em>-xylene, and <em>p</em>-xylene) in a single adsorption process. Individual adsorption measurements show complete exclusion of <em>o</em>-xylene and benchmark adsorption of other BTEXs. Competitive adsorption studies reveal record-high adsorption selectivity of other BTEXs over <em>o</em>-xylene. Vapor-phase breakthrough experiments verify its superior separation potential for sieving <em>o</em>-xylene from BTEXs. We further demonstrate <em>o</em>-xylene purification by simply soaking JNU-2 (10 g) in BTEXs (18 mL, 90% <em>o</em>-xylene) at room temperature, realizing an average of 15.2 mL of <em>o</em>-xylene (99.5%+ purity, 94% recovery) for 10 cycles. Considering its exceptional stability, JNU-2 may have great promise for energy-efficient <em>o</em>-xylene separation from BTEXs.","PeriodicalId":268,"journal":{"name":"Chem","volume":"8 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562007","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}
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