Pub Date : 2024-07-03Epub Date: 2024-06-14DOI: 10.1021/jacs.4c04716
Morgan S Young, Anne M LaPointe, Samantha N MacMillan, Geoffrey W Coates
Herein, we report that (S,S)-prophenolMg2(μ-OnBu)(THF)2 ((S,S)-1, prophenol = (S,S)-2,6-bis[2-(hydroxydiphenylmethyl)pyrrolidin-1-ylmethyl]-4-methylphenol) is a highly enantioselective (kR/kS = 140) precatalyst for ring-opening polymerization of rac-β-butyrolactone (β-BL) to isotactic poly(3-hydroxybutyrate) (i-PHB), a high performance, biodegradable polyester. Precatalyst (S,S)-1 polymerizes (R)-β-BL with an inversion of stereochemistry to (S)-PHB with a m% (percentage of adjacent linkages with a meso configuration) of 98% at 41% conversion and Tm of 165 °C under a variety of conditions. Complex (S,S)-1 demonstrates unique polymerization kinetics, as it does not polymerize the preferred enantiomer, (R)-β-BL, alone. Mechanistic studies revealed that (S)-β-BL is needed to convert (S,S)-1 into the active enantioselective polymerization catalyst. To the best of our knowledge, (S,S)-1 produces i-PHB with the highest degree of isotacticity observed from a polymerization of rac-β-BL. This study informs the design and understanding of future enantioselective and earth-abundant metal catalysts for ring-opening polymerization of β-lactones.
{"title":"Highly Enantioselective Polymerization of β-Butyrolactone by a Bimetallic Magnesium Catalyst: An Interdependent Relationship Between Favored and Unfavored Enantiomers.","authors":"Morgan S Young, Anne M LaPointe, Samantha N MacMillan, Geoffrey W Coates","doi":"10.1021/jacs.4c04716","DOIUrl":"10.1021/jacs.4c04716","url":null,"abstract":"<p><p>Herein, we report that (<i>S</i>,<i>S</i>)-prophenolMg<sub>2</sub>(μ-O<sup><i>n</i></sup>Bu)(THF)<sub>2</sub> ((<i>S</i>,<i>S</i>)-<b>1</b>, prophenol = (<i>S</i>,<i>S</i>)-2,6-bis[2-(hydroxydiphenylmethyl)pyrrolidin-1-ylmethyl]-4-methylphenol) is a highly enantioselective (<i>k</i><sub>R</sub>/<i>k</i><sub>S</sub> = 140) precatalyst for ring-opening polymerization of <i>rac</i>-β-butyrolactone (β-BL) to isotactic poly(3-hydroxybutyrate) (<i>i</i>-PHB), a high performance, biodegradable polyester. Precatalyst (<i>S</i>,<i>S</i>)-<b>1</b> polymerizes (<i>R</i>)-β-BL with an inversion of stereochemistry to (<i>S</i>)<i>-</i>PHB with a <i>m</i>% (percentage of adjacent linkages with a <i>meso</i> configuration) of 98% at 41% conversion and <i>T</i><sub>m</sub> of 165 °C under a variety of conditions. Complex (<i>S</i>,<i>S</i>)-<b>1</b> demonstrates unique polymerization kinetics, as it does not polymerize the preferred enantiomer, (<i>R</i>)-β-BL, alone. Mechanistic studies revealed that (<i>S</i>)-β-BL is needed to convert (<i>S</i>,<i>S</i>)-<b>1</b> into the active enantioselective polymerization catalyst. To the best of our knowledge, (<i>S</i>,<i>S</i>)-<b>1</b> produces <i>i</i>-PHB with the highest degree of isotacticity observed from a polymerization of <i>rac</i>-β-BL. This study informs the design and understanding of future enantioselective and earth-abundant metal catalysts for ring-opening polymerization of β-lactones.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141316077","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 : 2024-07-03Epub Date: 2024-06-20DOI: 10.1021/jacs.4c03534
Yifan Liao, Baptiste Le Roi, Hang Zhang, Charles E Diesendruck, Joshua M Grolman
Mechanical forces play critical roles in a wide variety of biological processes and diseases, yet measuring them directly at the molecular level remains one of the main challenges of mechanobiology. Here, we show a strategy to "Dip-conjugate" biologically derived materials at the chemical level to mechanophores, force-responsive molecular entities, using Click-chemistry. Contrary to classical prepolymerization mechanophore incorporation, this new protocol leads to detectable mechanochromic response with as low as 5% strain, finally making mechanophores relevant for many biological processes that have previously been inaccessible. Our results demonstrate the ubiquity of the technique with activation in synthetic polymers, carbohydrates, and proteins under mechanical force, with alpaca wool fibers as a key example. These results push the limits for mechanophore use in far more types of polymeric materials in applications ranging from molecular-level force damage detection to direct and quantitative 3D force measurements in mechanobiology.
{"title":"Facile Mechanophore Integration in Heterogeneous Biologically Derived Materials via \"Dip-Conjugation\".","authors":"Yifan Liao, Baptiste Le Roi, Hang Zhang, Charles E Diesendruck, Joshua M Grolman","doi":"10.1021/jacs.4c03534","DOIUrl":"10.1021/jacs.4c03534","url":null,"abstract":"<p><p>Mechanical forces play critical roles in a wide variety of biological processes and diseases, yet measuring them directly at the molecular level remains one of the main challenges of mechanobiology. Here, we show a strategy to \"Dip-conjugate\" biologically derived materials at the chemical level to mechanophores, force-responsive molecular entities, using Click-chemistry. Contrary to classical prepolymerization mechanophore incorporation, this new protocol leads to detectable mechanochromic response with as low as 5% strain, finally making mechanophores relevant for many biological processes that have previously been inaccessible. Our results demonstrate the ubiquity of the technique with activation in synthetic polymers, carbohydrates, and proteins under mechanical force, with alpaca wool fibers as a key example. These results push the limits for mechanophore use in far more types of polymeric materials in applications ranging from molecular-level force damage detection to direct and quantitative 3D force measurements in mechanobiology.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425662","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 : 2024-07-03Epub Date: 2024-06-20DOI: 10.1021/jacs.4c02463
Jinyan Luo, Quan Gao, Kui Tan, Shiling Zhang, Weiwei Shi, Lei Luo, Zhiying Li, Ghada E Khedr, Jie Chen, Youwei Xu, Ming Luo, Qi Xing, Jin Geng
Targeted protein degradation technology holds great potential in biomedicine, particularly in treating tumors and other protein-related diseases. Research on intracellular protein degradation using molecular glues and PROTAC technology is leading, while research on the degradation of membrane proteins and extracellular proteins through the lysosomal pathway is still in the preclinical stage. The scarcity of useful targets is an immense limitation to technological advancement, making it essential to explore novel, potentially effective approaches for targeted lysosomal degradation. Here, we employed the glucose transporter Glut1 as an innovative lysosome-targeting receptor and devised the Glut1-Facilitated Lysosomal Degradation (GFLD) strategy. We synthesized potential Glut1 ligands via reversible addition-fragmentation chain transfer (RAFT) polymerization and acquired antibody-glycooligomer conjugates through bioorthogonal reactions as lysosome-targeting protein degradation molecules, utilized in the management of PD-L1 high-expressing triple-negative breast cancer. The glucose transporter Glut1 as a lysosome-targeting receptor exhibits potential for the advancement of a broader array of medications in the future.
{"title":"Lysosome Targeting Chimaeras for Glut1-Facilitated Targeted Protein Degradation.","authors":"Jinyan Luo, Quan Gao, Kui Tan, Shiling Zhang, Weiwei Shi, Lei Luo, Zhiying Li, Ghada E Khedr, Jie Chen, Youwei Xu, Ming Luo, Qi Xing, Jin Geng","doi":"10.1021/jacs.4c02463","DOIUrl":"10.1021/jacs.4c02463","url":null,"abstract":"<p><p>Targeted protein degradation technology holds great potential in biomedicine, particularly in treating tumors and other protein-related diseases. Research on intracellular protein degradation using molecular glues and PROTAC technology is leading, while research on the degradation of membrane proteins and extracellular proteins through the lysosomal pathway is still in the preclinical stage. The scarcity of useful targets is an immense limitation to technological advancement, making it essential to explore novel, potentially effective approaches for targeted lysosomal degradation. Here, we employed the glucose transporter Glut1 as an innovative lysosome-targeting receptor and devised the Glut1-Facilitated Lysosomal Degradation (GFLD) strategy. We synthesized potential Glut1 ligands via reversible addition-fragmentation chain transfer (RAFT) polymerization and acquired antibody-glycooligomer conjugates through bioorthogonal reactions as lysosome-targeting protein degradation molecules, utilized in the management of PD-L1 high-expressing triple-negative breast cancer. The glucose transporter Glut1 as a lysosome-targeting receptor exhibits potential for the advancement of a broader array of medications in the future.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141425663","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 : 2024-07-03Epub Date: 2024-06-21DOI: 10.1021/jacs.4c05115
Marco Todisco, Aleksandar Radakovic, Jack W Szostak
Multiple RNA strands can interact in solution and assume a large variety of configurations dictated by their potential for base pairing. Although duplex formation from two complementary oligonucleotides has been studied in detail, we still lack a systematic characterization of the behavior of higher order complexes. Here, we focus on the thermodynamic and kinetic effects of an upstream oligonucleotide on the binding of a downstream oligonucleotide to a common template, as we vary the sequence and structure of the contact interface. We show that coaxial stacking in RNA is well correlated with but much more stabilizing than helix propagation over an analogous intact double helix step (median ΔΔG°37 °C ≈ 1.7 kcal/mol). Consequently, approximating coaxial stacking in RNA with the helix propagation term leads to large discrepancies between predictions and our experimentally determined melting temperatures, with an offset of ≈10 °C. Our kinetic study reveals that the hybridization of the downstream probe oligonucleotide is impaired (lower kon) by the presence of the upstream oligonucleotide, with the thermodynamic stabilization coming entirely from an extended lifetime (lower koff) of the bound downstream oligonucleotide, which can increase from seconds to months. Surprisingly, we show that the effect of nicks is dependent on the length of the stacking oligonucleotides, and we discuss the binding of ultrashort (1-4 nt) oligonucleotides that are relevant in the context of the origin of life. The thermodynamic and kinetic data obtained in this work allow for the prediction of the formation and stability of higher-order multistranded complexes.
{"title":"RNA Complexes with Nicks and Gaps: Thermodynamic and Kinetic Effects of Coaxial Stacking and Dangling Ends.","authors":"Marco Todisco, Aleksandar Radakovic, Jack W Szostak","doi":"10.1021/jacs.4c05115","DOIUrl":"10.1021/jacs.4c05115","url":null,"abstract":"<p><p>Multiple RNA strands can interact in solution and assume a large variety of configurations dictated by their potential for base pairing. Although duplex formation from two complementary oligonucleotides has been studied in detail, we still lack a systematic characterization of the behavior of higher order complexes. Here, we focus on the thermodynamic and kinetic effects of an upstream oligonucleotide on the binding of a downstream oligonucleotide to a common template, as we vary the sequence and structure of the contact interface. We show that coaxial stacking in RNA is well correlated with but much more stabilizing than helix propagation over an analogous intact double helix step (median ΔΔ<i>G</i>°<sub>37 °C</sub> ≈ 1.7 kcal/mol). Consequently, approximating coaxial stacking in RNA with the helix propagation term leads to large discrepancies between predictions and our experimentally determined melting temperatures, with an offset of ≈10 °C. Our kinetic study reveals that the hybridization of the downstream probe oligonucleotide is impaired (lower <i>k</i><sub>on</sub>) by the presence of the upstream oligonucleotide, with the thermodynamic stabilization coming entirely from an extended lifetime (lower <i>k</i><sub>off</sub>) of the bound downstream oligonucleotide, which can increase from seconds to months. Surprisingly, we show that the effect of nicks is dependent on the length of the stacking oligonucleotides, and we discuss the binding of ultrashort (1-4 nt) oligonucleotides that are relevant in the context of the origin of life. The thermodynamic and kinetic data obtained in this work allow for the prediction of the formation and stability of higher-order multistranded complexes.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430903","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 : 2024-07-03Epub Date: 2024-06-22DOI: 10.1021/jacs.4c06049
Shanshan Tao, Donglin Jiang
Covalent organic frameworks (COFs) offer an irreplaceable platform for mass transport, as they provide aligned one-dimensional channels as pathways. Especially, proton conduction is of great scientific interest and technological importance. However, unlike proton conduction under humidity, anhydrous proton conduction remains a challenge, as it requires robust materials and proceeds under harsh conditions. Here, we report exceptional anhydrous proton conduction in stable crystalline porous COFs by integrating neat phosphoric acid into the channels to form extended hydrogen-bonding networks. The phosphoric acid networks in the pores are stabilized by hierarchical multipoint and multichain hydrogen-bonding interactions with the 3D channel walls. We synthesized five hexagonal COFs that possess different pore sizes, which are gradually tuned from micropores to mesopores. Remarkably, mesoporous COFs with a high pore volume exhibit an exceptional anhydrous proton conductivity of 0.31 S cm-1, which marks the highest conductivity among all examples reported for COFs. We observed that the proton conductivity is dependent on the pore volume, pore size, and content of phosphoric acid. Increasing the pore volume improves the proton conductivity in an exponential fashion. Remarkably, changing the pore volume from 0.41 to 1.60 cm3 g-1 increases the proton conductivity by 1150-fold. Interestingly, as the pore size increases, the activation energy barrier of proton conduction decreases in linear mode. The mesopores enable fast proton hopping across the channels, while the micropores follow sluggish vehicle conduction. Experiments on tuning phosphoric acid loading contents revealed that a well-developed hydrogen-bonding phosphoric acid network in the pores is critical for proton conduction.
{"title":"Exceptional Anhydrous Proton Conduction in Covalent Organic Frameworks.","authors":"Shanshan Tao, Donglin Jiang","doi":"10.1021/jacs.4c06049","DOIUrl":"10.1021/jacs.4c06049","url":null,"abstract":"<p><p>Covalent organic frameworks (COFs) offer an irreplaceable platform for mass transport, as they provide aligned one-dimensional channels as pathways. Especially, proton conduction is of great scientific interest and technological importance. However, unlike proton conduction under humidity, anhydrous proton conduction remains a challenge, as it requires robust materials and proceeds under harsh conditions. Here, we report exceptional anhydrous proton conduction in stable crystalline porous COFs by integrating neat phosphoric acid into the channels to form extended hydrogen-bonding networks. The phosphoric acid networks in the pores are stabilized by hierarchical multipoint and multichain hydrogen-bonding interactions with the 3D channel walls. We synthesized five hexagonal COFs that possess different pore sizes, which are gradually tuned from micropores to mesopores. Remarkably, mesoporous COFs with a high pore volume exhibit an exceptional anhydrous proton conductivity of 0.31 S cm<sup>-1</sup>, which marks the highest conductivity among all examples reported for COFs. We observed that the proton conductivity is dependent on the pore volume, pore size, and content of phosphoric acid. Increasing the pore volume improves the proton conductivity in an exponential fashion. Remarkably, changing the pore volume from 0.41 to 1.60 cm<sup>3</sup> g<sup>-1</sup> increases the proton conductivity by 1150-fold. Interestingly, as the pore size increases, the activation energy barrier of proton conduction decreases in linear mode. The mesopores enable fast proton hopping across the channels, while the micropores follow sluggish vehicle conduction. Experiments on tuning phosphoric acid loading contents revealed that a well-developed hydrogen-bonding phosphoric acid network in the pores is critical for proton conduction.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141440063","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}
Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO2 reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO2-to-CO conversions (9.9 μmol h-1 CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 μmol h-1 and 42.8%).
晶体到玻璃的转化是调节晶体化学和物理特性的有力方法。在这里,我们证明了普鲁士蓝类似物之一的六氰基铁酸钴晶体的玻璃化转变在保持配位几何和短程有序结构的同时,增加了开放金属位点的浓度并改变了电子状态。通过 X 射线吸收精细结构、能量色散 X 射线光谱和 X 射线全散射对成分和结构变化进行了表征。这些变化使玻璃的平带电位变得更接近二氧化碳还原的氧化还原电位。玻璃的价带能也发生了变化,导致带隙能降低。与晶体对应物(3.9 μmol h-1 和 42.8%)相比,玻璃化后增加的开放金属位点和最佳电子结构提高了光催化活性,实现了 CO2 到 CO 的转化(9.9 μmol h-1 CO 生成量)和选择性(72.4%)。
{"title":"Prussian Blue Analogue Glasses for Photoinduced CO<sub>2</sub> Conversion.","authors":"Soracha Kosasang, Nattapol Ma, Sarawoot Impeng, Sareeya Bureekaew, Yuji Namiki, Masahiko Tsujimoto, Taya Saothayanun, Hiroki Yamada, Satoshi Horike","doi":"10.1021/jacs.4c03149","DOIUrl":"10.1021/jacs.4c03149","url":null,"abstract":"<p><p>Crystal-to-glass transformation is a powerful approach to modulating the chemical and physical properties of crystals. Here we demonstrate that the glass transformation of cobalt hexacyanoferrate crystals, one of the Prussian blue analogues, increased the concentration of open metal sites and altered the electronic state while maintaining coordination geometries and short-range ordering in the structure. The compositional and structural changes were characterized by X-ray absorption fine structure, energy dispersive X-ray spectroscopy, and X-ray total scattering. The changes contribute to the flat band potential of the glass becoming closer to the redox potential of CO<sub>2</sub> reduction. The valence band energy of the glass also shifts, resulting in lower band gap energy. Both the increased open metal sites and the optimal electronic structure upon vitrification enhance photocatalytic activity toward CO<sub>2</sub>-to-CO conversions (9.9 μmol h<sup>-1</sup> CO production) and selectivity (72.4%) in comparison with the crystalline counterpart (3.9 μmol h<sup>-1</sup> and 42.8%).</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141441776","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 : 2024-07-03Epub Date: 2024-06-25DOI: 10.1021/jacs.4c06068
Andrey Aslandukov, Akun Liang, Amanda Ehn, Florian Trybel, Yuqing Yin, Alena Aslandukova, Fariia I Akbar, Umbertoluca Ranieri, James Spender, Ross T Howie, Eleanor Lawrence Bright, Jonathan Wright, Michael Hanfland, Gaston Garbarino, Mohamed Mezouar, Timofey Fedotenko, Igor A Abrikosov, Natalia Dubrovinskaia, Leonid Dubrovinsky, Dominique Laniel
Inorganic ternary metal-C-N compounds with covalently bonded C-N anions encompass important classes of solids such as cyanides and carbodiimides, well known at ambient conditions and composed of [CN]- and [CN2]2- anions, as well as the high-pressure formed guanidinates featuring [CN3]5- anion. At still higher pressures, carbon is expected to be 4-fold coordinated by nitrogen atoms, but hitherto, such CN4-built anions are missing. In this study, four polycarbonitride compounds (LaCN3, TbCN3, CeCN5, and TbCN5) are synthesized in laser-heated diamond anvil cells at pressures between 90 and 111 GPa. Synchrotron single-crystal X-ray diffraction (SCXRD) reveals that their crystal structures are built of a previously unobserved anionic single-bonded carbon-nitrogen three-dimensional (3D) framework consisting of CN4 tetrahedra connected via di- or oligo-nitrogen linkers. A crystal-chemical analysis demonstrates that these polycarbonitride compounds have similarities to lanthanide silicon phosphides. Decompression experiments reveal the existence of LaCN3 and CeCN5 compounds over a very large pressure range. Density functional theory (DFT) supports these discoveries and provides further insight into the stability and physical properties of the synthesized compounds.
{"title":"Synthesis of LaCN<sub>3</sub>, TbCN<sub>3</sub>, CeCN<sub>5</sub>, and TbCN<sub>5</sub> Polycarbonitrides at Megabar Pressures.","authors":"Andrey Aslandukov, Akun Liang, Amanda Ehn, Florian Trybel, Yuqing Yin, Alena Aslandukova, Fariia I Akbar, Umbertoluca Ranieri, James Spender, Ross T Howie, Eleanor Lawrence Bright, Jonathan Wright, Michael Hanfland, Gaston Garbarino, Mohamed Mezouar, Timofey Fedotenko, Igor A Abrikosov, Natalia Dubrovinskaia, Leonid Dubrovinsky, Dominique Laniel","doi":"10.1021/jacs.4c06068","DOIUrl":"10.1021/jacs.4c06068","url":null,"abstract":"<p><p>Inorganic ternary metal-C-N compounds with covalently bonded C-N anions encompass important classes of solids such as cyanides and carbodiimides, well known at ambient conditions and composed of [CN]<sup>-</sup> and [CN<sub>2</sub>]<sup>2-</sup> anions, as well as the high-pressure formed guanidinates featuring [CN<sub>3</sub>]<sup>5-</sup> anion. At still higher pressures, carbon is expected to be 4-fold coordinated by nitrogen atoms, but hitherto, such CN<sub>4</sub>-built anions are missing. In this study, four polycarbonitride compounds (LaCN<sub>3</sub>, TbCN<sub>3</sub>, CeCN<sub>5</sub>, and TbCN<sub>5</sub>) are synthesized in laser-heated diamond anvil cells at pressures between 90 and 111 GPa. Synchrotron single-crystal X-ray diffraction (SCXRD) reveals that their crystal structures are built of a previously unobserved anionic single-bonded carbon-nitrogen three-dimensional (3D) framework consisting of CN<sub>4</sub> tetrahedra connected via di- or oligo-nitrogen linkers. A crystal-chemical analysis demonstrates that these polycarbonitride compounds have similarities to lanthanide silicon phosphides. Decompression experiments reveal the existence of LaCN<sub>3</sub> and CeCN<sub>5</sub> compounds over a very large pressure range. Density functional theory (DFT) supports these discoveries and provides further insight into the stability and physical properties of the synthesized compounds.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445500","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 : 2024-07-03Epub Date: 2024-06-25DOI: 10.1021/jacs.4c01654
Momoka Kimoto, Shoichi Sugiyama, Keigo Kumano, Satoshi Inagaki, Suguru Ito
Despite recent advances in porous organic molecular crystals, the engineering of dual-pore systems within the intermolecular voids remains a significant challenge. In this study, we have achieved the crystallization-induced social self-sorting of "quasi-racemic" dialdehydes into a macrocyclic imine. X-ray crystallographic analysis unambiguously characterizes the resulting structure as incorporating two quasi-racemate pairs with four diamine molecules. Notably, different alkyl substituents on the quasi-racemates afford two types of one-dimensional pores within the macrocyclic imine crystal. The different adsorption properties of these pores were substantiated through adsorption experiments. An intriguing helical arrangement of guest molecules was observed within one of the pores. This study provides pioneering evidence that the social self-sorting of quasi-racemates offers a new methodology for creating dual-functional supramolecular materials.
{"title":"Social Self-Sorting of Quasi-Racemates: A Unique Approach for Dual-Pore Molecular Crystals.","authors":"Momoka Kimoto, Shoichi Sugiyama, Keigo Kumano, Satoshi Inagaki, Suguru Ito","doi":"10.1021/jacs.4c01654","DOIUrl":"10.1021/jacs.4c01654","url":null,"abstract":"<p><p>Despite recent advances in porous organic molecular crystals, the engineering of dual-pore systems within the intermolecular voids remains a significant challenge. In this study, we have achieved the crystallization-induced social self-sorting of \"quasi-racemic\" dialdehydes into a macrocyclic imine. X-ray crystallographic analysis unambiguously characterizes the resulting structure as incorporating two quasi-racemate pairs with four diamine molecules. Notably, different alkyl substituents on the quasi-racemates afford two types of one-dimensional pores within the macrocyclic imine crystal. The different adsorption properties of these pores were substantiated through adsorption experiments. An intriguing helical arrangement of guest molecules was observed within one of the pores. This study provides pioneering evidence that the social self-sorting of quasi-racemates offers a new methodology for creating dual-functional supramolecular materials.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141445586","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}
Single-molecule junctions, formed by a single molecule bridging a gap between two metal electrodes, are attracting attention as basic models of ultrasmall electronic devices. Although charge transport through π-conjugated molecules with π-delocalized system has been widely studied for a number of molecular junctions, there has been almost no research on charge transport through molecular junctions with a σ-delocalized orbital system. Compounds with hexa-selenium-substituted benzene form a σ-delocalized orbital system on the periphery of the benzene ring. In this study, we fabricated single-molecule junctions with the σ-delocalized orbital systems arising from lone-pair interactions of selenium atoms and clarified their electronic properties using the break-junction method. The single-molecule junctions with the σ-orbital systems show efficient charge transport properties and can be one of the alternatives to those with conventional π-orbital systems as minute electronic conductors.
{"title":"Charge Transport through Single-Molecule Junctions with σ-Delocalized Systems.","authors":"Shintaro Fujii, Saya Seko, Taichi Tanaka, Yuki Yoshihara, Shunsuke Furukawa, Tomoaki Nishino, Masaichi Saito","doi":"10.1021/jacs.4c06732","DOIUrl":"https://doi.org/10.1021/jacs.4c06732","url":null,"abstract":"<p><p>Single-molecule junctions, formed by a single molecule bridging a gap between two metal electrodes, are attracting attention as basic models of ultrasmall electronic devices. Although charge transport through π-conjugated molecules with π-delocalized system has been widely studied for a number of molecular junctions, there has been almost no research on charge transport through molecular junctions with a σ-delocalized orbital system. Compounds with hexa-selenium-substituted benzene form a σ-delocalized orbital system on the periphery of the benzene ring. In this study, we fabricated single-molecule junctions with the σ-delocalized orbital systems arising from lone-pair interactions of selenium atoms and clarified their electronic properties using the break-junction method. The single-molecule junctions with the σ-orbital systems show efficient charge transport properties and can be one of the alternatives to those with conventional π-orbital systems as minute electronic conductors.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489960","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}
Jake J Blackner, Olivia M Schneider, Warren O Wong, Dennis G Hall
The design of small molecules with unique geometric profiles or molecular connectivity represents an intriguing yet neglected challenge in modern organic synthesis. This challenge is compounded when emphasis is placed on the preparation of new chemotypes that have distinct and practical functions. To expand the structural diversity of boron-containing heterocycles, we report herein the preparation of novel monocyclic hemiboronic acids, diazaborines. These compounds have enabled the study of a pseudoaromatic boranol-containing (B-OH) ring free of influence from an appended aromatic system. Synthetic and spectroscopic studies have provided insight into the aromatic character, Lewis acidic nature, chemical reactivity, and unique ability of the exocyclic B-OH unit to participate in hydroxy exchange, suggesting their use in organocatalysis and as reversible covalent inhibitors. Moreover, density functional theory and nucleus-independent chemical shift calculations reveal that the aromatic character of the boroheterocyclic ring is increased significantly in comparison to known bicyclic benzodiazaborines (naphthoid congeners), consequently leading to attenuated Lewis acidity. Direct structural comparison to a well-established biaryl isostere, 2-phenylphenol, through X-ray crystallographic analysis reveals that N-aryl derivatives are strikingly similar in size and conformation, with attenuated logP values underscoring the value of the polar BNN unit. Their potential application as low-molecular-weight scaffolds in drug discovery is demonstrated through orthogonal diversification and preliminary antifungal evaluation (Candida albicans), which unveiled analogs with low micromolar inhibitory concentration.
{"title":"Removing Neighboring Ring Influence in Monocyclic B-OH Diazaborines: Properties and Reactivity as Phenolic Bioisosteres with Dynamic Hydroxy Exchange.","authors":"Jake J Blackner, Olivia M Schneider, Warren O Wong, Dennis G Hall","doi":"10.1021/jacs.4c06360","DOIUrl":"https://doi.org/10.1021/jacs.4c06360","url":null,"abstract":"<p><p>The design of small molecules with unique geometric profiles or molecular connectivity represents an intriguing yet neglected challenge in modern organic synthesis. This challenge is compounded when emphasis is placed on the preparation of new chemotypes that have distinct and practical functions. To expand the structural diversity of boron-containing heterocycles, we report herein the preparation of novel monocyclic hemiboronic acids, diazaborines. These compounds have enabled the study of a pseudoaromatic boranol-containing (B-OH) ring free of influence from an appended aromatic system. Synthetic and spectroscopic studies have provided insight into the aromatic character, Lewis acidic nature, chemical reactivity, and unique ability of the exocyclic B-OH unit to participate in hydroxy exchange, suggesting their use in organocatalysis and as reversible covalent inhibitors. Moreover, density functional theory and nucleus-independent chemical shift calculations reveal that the aromatic character of the boroheterocyclic ring is increased significantly in comparison to known bicyclic benzodiazaborines (naphthoid congeners), consequently leading to attenuated Lewis acidity. Direct structural comparison to a well-established biaryl isostere, 2-phenylphenol, through X-ray crystallographic analysis reveals that <i>N</i>-aryl derivatives are strikingly similar in size and conformation, with attenuated log<i>P</i> values underscoring the value of the polar BNN unit. Their potential application as low-molecular-weight scaffolds in drug discovery is demonstrated through orthogonal diversification and preliminary antifungal evaluation (<i>Candida albicans</i>), which unveiled analogs with low micromolar inhibitory concentration.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141489974","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}