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Grappa – a machine learned molecular mechanics force field

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-15 DOI: 10.1039/d4sc05465b

Leif Seute, Eric Hartmann, Jan Stühmer, Frauke Gräter

Simulating large molecular systems over long timescales requires force fields that are both accurate and efficient. In recent years, E(3) equivariant neural networks have lifted the tension between computational efficiency and accuracy of force fields, but they are still several orders of magnitude more expensive than established molecular mechanics (MM) force fields. Here, we propose Grappa, a machine learning framework to predict MM parameters from the molecular graph, employing a graph attentional neural network and a transformer with symmetry-preserving positional encoding. The resulting Grappa force field outperforms tabulated and machine-learned MM force fields in terms of accuracy at the same computational efficiency and can be used in existing Molecular Dynamics (MD) engines like GROMACS and OpenMM. It predicts energies and forces of small molecules, peptides, and RNA at state-of-the-art MM accuracy, while also reproducing experimentally measured values for J-couplings. With its simple input features and high data-efficiency, Grappa is well suited for extensions to uncharted regions of chemical space, which we show on the example of peptide radicals. We demonstrate Grappa's transferability to macromolecules in MD simulations from a small fast-folding protein up to a whole virus particle. Our force field sets the stage for biomolecular simulations closer to chemical accuracy, but with the same computational cost as established protein force fields.

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引用次数: 0

Periodic Law-Guided Design of Highly Stable O3-Type Layered Oxide Cathodes for Practical Sodium-Ion Batteries

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-15 DOI: 10.1039/d4sc08351b

Yuan-Bo Wu, Hai-Yan Hu, Jia-Yang Li, Hanghang Dong, Yan-Fang Zhu, Shuangqiang Chen, Nana Wang, Jiazhao Wang, Yao Xiao

O3-type NaNi0.5Mn0.5O2 cathode material exhibits significant potential for sodium-ion batteries (SIBs) owing to its high theoretical capacity and ample sodium reservoir. Nonetheless, its practical implementation encounters considerable obstacles, such as impaired structural integrity, sensitivity to moisture, inadequate high temperature stability, and unstable at high voltage conditions. This study investigates the co-substitution of Cu, Mg, and Ti, guided by principles of the periodic law, to enhance the material’s stability under varying conditions. The substituent elements were selected based on their atomic properties and introduced into specific sites within the structure: Cu and Mg were substituted at Ni sites, while Ti replaced Mn sites. These modifications strengthened the crystal lattice, mitigating phase transitions, and improved electrochemical performance. The O3- NaNi0.4Cu0.05Mg0.05Mn0.3Ti0.2O2 material exhibited remarkable moisture stability, maintaining 85% of its capacity after 1000 cycles at 5C in 2.0–4.0 V. It also exhibited reversible phase transitions at voltages up to 4.3 V, with no oxygen release observed even when charged to 4.5 V. Furthermore, it exhibited remarkable high-temperature stability in half-cell testing and excellent cycle performance in full-cell evaluations. These results are very helpful for designing high-performance SIB cathodes that can withstand a variety of operating circumstances and ensuring structural stability.

{"title":"Periodic Law-Guided Design of Highly Stable O3-Type Layered Oxide Cathodes for Practical Sodium-Ion Batteries","authors":"Yuan-Bo Wu, Hai-Yan Hu, Jia-Yang Li, Hanghang Dong, Yan-Fang Zhu, Shuangqiang Chen, Nana Wang, Jiazhao Wang, Yao Xiao","doi":"10.1039/d4sc08351b","DOIUrl":"https://doi.org/10.1039/d4sc08351b","url":null,"abstract":"O3-type NaNi0.5Mn0.5O2 cathode material exhibits significant potential for sodium-ion batteries (SIBs) owing to its high theoretical capacity and ample sodium reservoir. Nonetheless, its practical implementation encounters considerable obstacles, such as impaired structural integrity, sensitivity to moisture, inadequate high temperature stability, and unstable at high voltage conditions. This study investigates the co-substitution of Cu, Mg, and Ti, guided by principles of the periodic law, to enhance the material’s stability under varying conditions. The substituent elements were selected based on their atomic properties and introduced into specific sites within the structure: Cu and Mg were substituted at Ni sites, while Ti replaced Mn sites. These modifications strengthened the crystal lattice, mitigating phase transitions, and improved electrochemical performance. The O3- NaNi0.4Cu0.05Mg0.05Mn0.3Ti0.2O2 material exhibited remarkable moisture stability, maintaining 85% of its capacity after 1000 cycles at 5C in 2.0–4.0 V. It also exhibited reversible phase transitions at voltages up to 4.3 V, with no oxygen release observed even when charged to 4.5 V. Furthermore, it exhibited remarkable high-temperature stability in half-cell testing and excellent cycle performance in full-cell evaluations. These results are very helpful for designing high-performance SIB cathodes that can withstand a variety of operating circumstances and ensuring structural stability.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"89 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981316","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

Photodegradation reveals that singlet energy transfer impedes energy-gradient-driven singlet ﬁssion in polyacene blends 光降解揭示出单线能量转移阻碍了聚乙炔共混物中由能量梯度驱动的单线能量消耗

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-14 DOI: 10.1039/d4sc06702a

Alexandra N. Stuart, Jessica de la Perrelle, David Mark Huang, Tak W. Kee

Singlet fission (SF) is a process that is potentially beneficial for photovoltaics by producing two triplet excitons from a single photon, but its application is often hindered by the inability to effectively separate the resultant triplet excitons. It has been proposed that an energy gradient can assist in separating triplet excitons through triplet energy transfer between chromophores of different triplet energies, but this approach has only been studied in solution and the efficacy of this strategy in the solid state is under explored. Here, we investigate energy-gradient-driven SF in a disordered solid state, in the form of suspensions of 5,12-bis(triisopropylsilylethnyl)tetracene:6,13-bis(triisopropylsilylethnyl)pentance (TIPS-Tn:TIPS-Pn) blend nanoparticles (NPs). Rather than using more conventional techniques such as ultrafast (sub-nanosecond) spectroscopy, we study the photophysics in these NPs through monitoring their photodegradation. TIPS-Tn photodegrades rapidly in neat NPs, but this photodegradation is suppressed upon the addition of TIPS-Pn, indicating a decrease in the TIPS-Tn triplet population. By modeling the photodegradation over a timescale of minutes to hours, we are able to reveal details of processes on the ultrafast timescale. We show that triplet energy transfer occurs from TIPS-Tn to TIPS-Pn, leading to slower photodegradation for TIPS-Tn, and faster photodegradation for TIPS-Pn. However, modeling additionally indicates that singlet energy transfer from TIPS-Tn to TIPS-Pn also occurs, and in fact acts to reduce the efficiency of TIPS-Tn SF. Hence, in this particular system, the energy gradient impedes SF, rather than assisting it. These findings indicate that chromophore pairs must be carefully selected to switch off singlet energy transfer for the energy-gradient approach to be effective in enhancing SF.

{"title":"Photodegradation reveals that singlet energy transfer impedes energy-gradient-driven singlet ﬁssion in polyacene blends","authors":"Alexandra N. Stuart, Jessica de la Perrelle, David Mark Huang, Tak W. Kee","doi":"10.1039/d4sc06702a","DOIUrl":"https://doi.org/10.1039/d4sc06702a","url":null,"abstract":"Singlet fission (SF) is a process that is potentially beneficial for photovoltaics by producing two triplet excitons from a single photon, but its application is often hindered by the inability to effectively separate the resultant triplet excitons. It has been proposed that an energy gradient can assist in separating triplet excitons through triplet energy transfer between chromophores of different triplet energies, but this approach has only been studied in solution and the efficacy of this strategy in the solid state is under explored. Here, we investigate energy-gradient-driven SF in a disordered solid state, in the form of suspensions of 5,12-bis(triisopropylsilylethnyl)tetracene:6,13-bis(triisopropylsilylethnyl)pentance (TIPS-Tn:TIPS-Pn) blend nanoparticles (NPs). Rather than using more conventional techniques such as ultrafast (sub-nanosecond) spectroscopy, we study the photophysics in these NPs through monitoring their photodegradation. TIPS-Tn photodegrades rapidly in neat NPs, but this photodegradation is suppressed upon the addition of TIPS-Pn, indicating a decrease in the TIPS-Tn triplet population. By modeling the photodegradation over a timescale of minutes to hours, we are able to reveal details of processes on the ultrafast timescale. We show that triplet energy transfer occurs from TIPS-Tn to TIPS-Pn, leading to slower photodegradation for TIPS-Tn, and faster photodegradation for TIPS-Pn. However, modeling additionally indicates that singlet energy transfer from TIPS-Tn to TIPS-Pn also occurs, and in fact acts to reduce the efficiency of TIPS-Tn SF. Hence, in this particular system, the energy gradient impedes SF, rather than assisting it. These findings indicate that chromophore pairs must be carefully selected to switch off singlet energy transfer for the energy-gradient approach to be effective in enhancing SF.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975509","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

Unravelling the pH-depended mechanism of ferroelectric polarization on different dynamic pathways of photoelectrochemical water oxidation 揭示铁电极化在光电化学水氧化的不同动态路径上的 pH 值依赖机制

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-14 DOI: 10.1039/d4sc08291e

Xing Ji, Zhouhao Zhu, Ming Zhou, Ying Zhang, Li-Yong Gan, Yunhuai Zhang, Peng Xiao

Ferroelectric polarization is considered to be an effective strategy capable of improving the oxygen evolution reaction (OER) of photoelectrocatalysis. The frontier challenge is to clarify how the polarization field control the OER dynamic pathway from molecular details. Here, using the electrochemical fingerprints tests together with theoretical calculations, we systematically investigate the free energy change of oxo and hydroxyl intermediates on TiO2-BaTiO3 core-shell nanowires (BTO@TiO₂) under polarization in different pH environments. We demonstrate that in the adsorbate evolution mechanism (AEM) dominated in acid environment, both positive and negative polarization result in a reduction of the oxo free energy, thereby inhibiting the reaction kinetics. In the oxide path mechanism (OPM) occurred mainly in alkaline condition, ferroelectric polarization exhibits a repulsive adsorbate-adsorbate interactions for OH- coverage and free energy shift of hydroxyl groups. We elucidate that a weakly alkaline electrolyte is the optimal application environment for ferroelectric polarization, the positive polarization promotes the OH- coverage and facilitate reaction pathway transfer from AEM to OPM, thus BTO@TiO2 exhibited a record polarization enhancement of 0.52 mA/cm2 at 1.23 VRHE in pH=11. This work provides a more accurate insights into the pH-depended effect of ferroelectric polarization on OER dynamic pathway than conventional models that are based solely on the band bending regulation.

铁电极化被认为是一种能够改善光电催化氧进化反应（OER）的有效策略。目前的前沿挑战是如何从分子细节上阐明极化场如何控制 OER 的动态路径。在此，我们利用电化学指纹测试和理论计算，系统地研究了不同 pH 值环境下极化条件下 TiO2-BaTiO3 核壳纳米线（BTO@TiO₂）上氧化和羟基中间产物的自由能变化。我们证明，在酸性环境中占主导地位的吸附剂进化机制（AEM）中，正极化和负极化都会导致氧化自由能降低，从而抑制反应动力学。在主要发生在碱性条件下的氧化物路径机制（OPM）中，铁电极化对羟基覆盖和羟基自由能移动表现出吸附剂与吸附剂之间的排斥作用。我们阐明了弱碱性电解质是铁电极化的最佳应用环境，正极化促进了 OH- 的覆盖，并促进了从 AEM 到 OPM 的反应路径转移，因此 BTO@TiO2 在 pH=11 的 1.23 VRHE 条件下显示出 0.52 mA/cm2 的创纪录极化增强。与传统的仅基于带弯曲调节的模型相比，这项工作更准确地揭示了铁电极化对 OER 动态通路的 pH 值依赖效应。

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引用次数: 0

Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion.

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-13 DOI: 10.1039/d4sc08255a

Yikun Zhu, Jan Borstelmann, Christian Neiss, Zheng Wei, Andreas Görling, Milan Kivala, Marina A Petrukhina

The chemical reduction of a pyracylene-hexa-peri-hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The in situ reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and ¹H NMR spectroscopy, evidenced the stepwise reduction process. The use of different solvents and secondary ligands enabled isolation of single crystals of three different reduced states of TPP with 1, 2, and 3 electrons added to its π-system. This provided a unique set of carbanions with gradually increasing negative charge for in-depth structural analysis of the outcomes of controlled electron addition to a non-planar and asymmetric nanographene, using X-ray crystallographic, spectroscopic, and theoretical tools. EPR spectroscopy measurements of the mono- and triply-reduced TPP products revealed distinct EPR splitting patterns. DFT calculations demonstrated a notable difference in the spin density distribution of these two open-shell products and provided insights into experimental EPR data. Moreover, the influence of the counterions on the "naked" TPP anions was illustrated computationally.

{"title":"Stepwise reduction of an asymmetric π-expanded pyracylene towards the crystalline radical trianion.","authors":"Yikun Zhu, Jan Borstelmann, Christian Neiss, Zheng Wei, Andreas Görling, Milan Kivala, Marina A Petrukhina","doi":"10.1039/d4sc08255a","DOIUrl":"https://doi.org/10.1039/d4sc08255a","url":null,"abstract":"The chemical reduction of a pyracylene-hexa-peri-hexabenzocoronene-(HBC)-fused nanographene TPP was investigated with K and Rb metals to reveal its multi-electron acceptor abilities. The in situ reaction of TPP with the above alkali metals, monitored by UV-vis-NIR and 1H NMR spectroscopy, evidenced the stepwise reduction process. The use of different solvents and secondary ligands enabled isolation of single crystals of three different reduced states of TPP with 1, 2, and 3 electrons added to its π-system. This provided a unique set of carbanions with gradually increasing negative charge for in-depth structural analysis of the outcomes of controlled electron addition to a non-planar and asymmetric nanographene, using X-ray crystallographic, spectroscopic, and theoretical tools. EPR spectroscopy measurements of the mono- and triply-reduced TPP products revealed distinct EPR splitting patterns. DFT calculations demonstrated a notable difference in the spin density distribution of these two open-shell products and provided insights into experimental EPR data. Moreover, the influence of the counterions on the \"naked\" TPP anions was illustrated computationally.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11744371/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143000712","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

Radical trifluoromethoxylation of fluorinated alkenes for accessing difluoro(trifluoromethoxy)methyl groups

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-13 DOI: 10.1039/d4sc07788a

Koki Kawai, Mai Usui, Sota Ikawa, Naoyuki Hoshiya, Yosuke Kishikawa, Norio Shibata

In this study, we explore the potential of the difluoro(trifluoromethoxy)methyl group, CF₂–O–CF₃, an underexplored but promising structural analog of the trifluoromethoxy group (OCF₃). This moiety offers unique electronic properties and enhanced chemical stability due to its multiple C–F bonds, along with the added advantage of C–O bond cleavage, making it an attractive option in fluorine chemistry. We have succeeded in synthesizing difluoro(trifluoromethoxy)methyl compounds via radical amino- and hydroxy-trifluoromethoxylations of β,β-difluorostyrenes. Control experiments, including radical clock experiments, support a free radical mechanism. The synthetic utility of the resulting difluoro(trifluoromethoxy)methyl compounds is also demonstrated through transformations into bioactive analogs, such as pyrrole derivatives, fendiline analogs, and carpropamid analogs, highlighting their potential in drug development.

引用次数: 0

Discovery of fully synthetic FKBP12-mTOR molecular glues

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-13 DOI: 10.1039/d4sc06917j

Robin C. E. Deutscher, Christian Meyners, Maximilian L. Repity, Wisely Oki Sugiarto, Jürgen M Kolos, Edvaldo Maciel, Tim Heymann, Thomas M. Geiger, Felix Hausch, Stefan Knapp, Frederik Lermyte

Molecular glues are a new drug modality with the potential to engage otherwise undruggable targets. However, the rational discovery of molecular glues for desired targets is a major challenge and most known molecular glues have been discovered by serendipity. Here we present the first fully synthetic FKBP12-mTOR molecular glues, which were discovered from a FKBP-focused, target-unbiased ligand library. Our biochemical screening of >1000 in-house FKBP ligands yielded one hit that induced dimerization of FKBP12 and the FRB domain of mTOR. The crystal structure of the ternary complex revealed that the hit targeted a similar surface on FRB domain compared to natural product rapamycin but with a radically different interaction pattern. Structure-guided optimization improved potency 500-fold and led to compounds, which initiate FKBP12-FRB complex formation in cells. Our results show that molecular glues targeting flat surfaces can be discovered by focused screening and support the use of FKBP12 as a versatile presenter protein for molecular glues.

{"title":"Discovery of fully synthetic FKBP12-mTOR molecular glues","authors":"Robin C. E. Deutscher, Christian Meyners, Maximilian L. Repity, Wisely Oki Sugiarto, Jürgen M Kolos, Edvaldo Maciel, Tim Heymann, Thomas M. Geiger, Felix Hausch, Stefan Knapp, Frederik Lermyte","doi":"10.1039/d4sc06917j","DOIUrl":"https://doi.org/10.1039/d4sc06917j","url":null,"abstract":"Molecular glues are a new drug modality with the potential to engage otherwise undruggable targets. However, the rational discovery of molecular glues for desired targets is a major challenge and most known molecular glues have been discovered by serendipity. Here we present the first fully synthetic FKBP12-mTOR molecular glues, which were discovered from a FKBP-focused, target-unbiased ligand library. Our biochemical screening of >1000 in-house FKBP ligands yielded one hit that induced dimerization of FKBP12 and the FRB domain of mTOR. The crystal structure of the ternary complex revealed that the hit targeted a similar surface on FRB domain compared to natural product rapamycin but with a radically different interaction pattern. Structure-guided optimization improved potency 500-fold and led to compounds, which initiate FKBP12-FRB complex formation in cells. Our results show that molecular glues targeting flat surfaces can be discovered by focused screening and support the use of FKBP12 as a versatile presenter protein for molecular glues.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968519","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

Photocatalytic [3 + 2]-annulation via sodium tetraarylborate: a fundamental approach for synthesizing 1,4,2-diazaborole analogs

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-13 DOI: 10.1039/d4sc08085h

Hao-Ni Qin, Hao-Wen Jiang, Yi Zhao, Saira Qurban, Ke-Chun Wang, Peng-Fei Xu

Substantial advancements have been achieved in the field of photocatalytic borylation utilizing 4c-7e Lewis base-boryl radicals. However, the utilization of 3c-5e neutral boryl radicals for C–B bond formation remains relatively underexplored due to their inherent instability. In this study, we successfully demonstrated the direct construction of C–B bonds using sodium tetraarylborate as a key reagent. This was accomplished by effectively stabilizing diaryl boryl radicals with nitrile compounds, thereby facilitating the synthesis of valuable boron-containing compounds. Overall, our research elucidates the significant role played by sodium tetraarylborate in enabling an efficient and versatile approach for synthesizing of 1,4,2-diazaborole analogs through a photocatalyzed [3 + 2]-annulation reaction. This mild and adaptable methodology expands synthetic strategies for obtaining diverse derivatives of 1,4,2-diazaboroles, with the RCN–BAr₂ complex serving as an effective boron–nitrogen synthon that opens up pathways to multiple boron–nitrogen heterocycles. Furthermore, this breakthrough significantly enhances the applicability of sodium tetraarylborate in photoredox catalysis.

{"title":"Photocatalytic [3 + 2]-annulation via sodium tetraarylborate: a fundamental approach for synthesizing 1,4,2-diazaborole analogs","authors":"Hao-Ni Qin, Hao-Wen Jiang, Yi Zhao, Saira Qurban, Ke-Chun Wang, Peng-Fei Xu","doi":"10.1039/d4sc08085h","DOIUrl":"https://doi.org/10.1039/d4sc08085h","url":null,"abstract":"Substantial advancements have been achieved in the field of photocatalytic borylation utilizing 4c-7e Lewis base-boryl radicals. However, the utilization of 3c-5e neutral boryl radicals for C–B bond formation remains relatively underexplored due to their inherent instability. In this study, we successfully demonstrated the direct construction of C–B bonds using sodium tetraarylborate as a key reagent. This was accomplished by effectively stabilizing diaryl boryl radicals with nitrile compounds, thereby facilitating the synthesis of valuable boron-containing compounds. Overall, our research elucidates the significant role played by sodium tetraarylborate in enabling an efficient and versatile approach for synthesizing of 1,4,2-diazaborole analogs through a photocatalyzed [3 + 2]-annulation reaction. This mild and adaptable methodology expands synthetic strategies for obtaining diverse derivatives of 1,4,2-diazaboroles, with the RCN–BAr2 complex serving as an effective boron–nitrogen synthon that opens up pathways to multiple boron–nitrogen heterocycles. Furthermore, this breakthrough significantly enhances the applicability of sodium tetraarylborate in photoredox catalysis.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968619","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

Competing pathways to aromaticity governed by amine dehydrogenation and metal-organic complexation in on-surface synthesis.

IF 7.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-13 DOI: 10.1039/d4sc07550a

Andrés Lombana, Songpol Chaunchaiyakul, Olivier Chuzel, Denis Hagebaum-Reignier, Jean-Luc Parrain, Franck Bocquet, Laurent Nony, Christian Loppacher, Federica Bondino, Elena Magnano, Hiroshi Imada, Emiko Kazuma, Yousoo Kim, Luca Giovanelli, Sylvain Clair

We investigated the reactivity of a gem-dichlorovinyl-carbazole precursor in the on-surface synthesis approach. Our findings reveal that, on the Au(111) surface, the thermally-induced dehalogenation reaction led to the formation of cumulene dimers. Contrastingly, the more reactive Cu(111) surface promoted the formation of a polyheterocyclic compound exhibiting extended aromaticity. The latter was found to be related to the dehydrogenation of the amine groups, which did not occur on Au(111), thus promoting the different reactivity observed. At higher annealing temperature, selective C-H activation led to the formation of well-defined organometallic chains. In addition, we found that the amine complexation with metal adatom on Cu(111) was an inhibiting factor for the dimerization reaction, a challenge that could be overcome through proper control of the deposition conditions.

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引用次数: 0

Exploring New Horizons in Mid-to-Far Infrared Nonlinear Optical Crystals: The Significant Potential of Trigonal Pyramidal [TeS3]²⁻ Functional Units

IF 8.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Chemical Science

Pub Date : 2025-01-10 DOI: 10.1039/d4sc07322c

Bo Zhang, Shenghua Zhou, Bing-Xuan Li, Xintao Wu, Hua Lin, Qi-Long Zhu

Traditional tetrahedral-based mid-to-far infrared (MFIR) nonlinear optical (NLO) crystals often face limitations due to the optical anisotropy constraints imposed by their highly symmetric structures. In contrast, the relatively rare trigonal pyramidal [TeS3]2- functional unit characterized by its asymmetric structure and stereochemically active lone pair (SCALP), offers improved optical anisotropy, hyperpolarizability and a broader IR transparency range. Despite its potential, synthetic challenges have hindered the development of MFIR NLO crystals that incorporate this unit, with only one example reported to date. Herein, an innovative MFIR NLO crystal, Cu10Te4S13 has been successfully constructed using the trigonal pyramidal [TeS3]²⁻ units, via a simple high-temperature solid-state method. The novel three-dimensional structure of Cu10Te4S13 is interconnected by butterfly-orchid-like [Cu6Te4S13] anionic clusters and [CuS4] groups, where the former are formed by trigonal pyramidal [TeS3]2- groups and [Cu6S13] hexamers. Cu10Te4S13 exhibits a remarkable second harmonic generation effect, approximately 3.75 times that of AgGaS₂ at 2900 nm at the particle size range of 30–45 μm. Additionally, it demonstrates favorable crystal growth habits, producing single crystals with maximum dimensions of about 7×3×2 mm³. This polished single crystal appears complete transparency within the MFIR spectral window ranging from 2.5 to 25 μm, representing the widest IR transmission in all reported NLO chalcogenides. Furthermore, the structure-property relationship is also elucidated through first-principles analysis. This work confirms the potential of the unique trigonal pyramidal [TeS3]2- as a MFIR NLO functional unit, paving the way for the development of unconventional MFIR NLO materials.

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引用次数: 0

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