ACS Organic & Inorganic Au最新文献

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Synthetic Access to Fluorinated Analogs of a Known Streptococcus pneumoniae Type 14 Glycotope. 已知肺炎链球菌14型糖基氟化类似物的合成途径
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2026-01-21 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00108
Maximilian Reindl, Andreas Baumann, Anja Hoffmann-Röder
{"title":"Synthetic Access to Fluorinated Analogs of a Known <i>Streptococcus pneumoniae</i> Type 14 Glycotope.","authors":"Maximilian Reindl, Andreas Baumann, Anja Hoffmann-Röder","doi":"10.1021/acsorginorgau.5c00108","DOIUrl":"10.1021/acsorginorgau.5c00108","url":null,"abstract":"<p><p>For the first time, we present fluorinated analogs of <i>Streptococcus pneumoniae</i> serotype 14 (SPn14)-specific tetrasaccharide antigens originating from the repeating unit {6)-[β-d-Gal<i>p</i>-(1→4)-]-β-d-Glc<i>p</i>NAc-(1→3)-β-d-Gal<i>p</i>-(1→4)-β-d-Glc<i>p</i>-(1→} <sub><i>n</i></sub> of the capsule's outer cell surface, featuring different strategic fluorination sites. These modified pneumococcal tetrasaccharides are also equipped with allyl groups at the reducing end to enable further functionalization. Key transformation steps during the synthesis of these target molecules included (1 + 1)-glycosylations of fluorinated galactosyl donors as well as late fluorination steps, which were selectively performed on lactosyl building blocks. The subsequent central (2 + 2) couplings of the lactosyl donors with the respective lactosaminyl building blocks proceeded with good yields, enabling the synthesis of the desired target tetrasaccharide antigen analogs in amounts sufficient for future biological investigations following a global deprotection protocol. A total of six novel F-analogs of the SPn14 glycotope were produced using the methods described herein.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"161-168"},"PeriodicalIF":3.3,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879181/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Deoxyfluorination of Hydroxy-Substituted Boronates. 羟基取代硼酸盐的脱氧氟化。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-12-31 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00112
Yaroslav Melnyk, Oleksandr S Liashuk, Oleksandr Horulya, Olexiy D Kachkovskiy, Oleksandr O Grygorenko
{"title":"Deoxyfluorination of Hydroxy-Substituted Boronates.","authors":"Yaroslav Melnyk, Oleksandr S Liashuk, Oleksandr Horulya, Olexiy D Kachkovskiy, Oleksandr O Grygorenko","doi":"10.1021/acsorginorgau.5c00112","DOIUrl":"10.1021/acsorginorgau.5c00112","url":null,"abstract":"<p><p>A practical and scalable protocol for the deoxyfluorination of hydroxyalkyl-substituted aryl- and alkenylboronates was developed. The optimized conditions (combining Deoxo-Fluor with TEA·3HF as the reagents and substrate preconversion to trifluoroborate salts) enabled efficient transformation across a wide range of (homo)-benzylic and allylic alcohols while tolerating protected carboxyl and amino groups. The resulting fluorinated boronates performed well as versatile building blocks in oxidation and Suzuki cross-coupling reactions. Furthermore, a telescoped one-pot strategy allowed direct utilization of crude fluorinated intermediates, enabling access to complex molecular frameworks containing alcohol, carbonyl, and ester functionalities, typically intolerant to late-stage fluorination conditions. This methodology offers a general and efficient route for the incorporation of monofluorinated aliphatic fragments into structures that are relevant for medicinal chemistry and materials science.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"169-176"},"PeriodicalIF":3.3,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879177/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unusual Magnetic Order in Eu11-x Hg54+x. Eu11-x中Hg54+x的异常磁序。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-12-22 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00099
Rachel Nixon, Nazar Zaremba, Samuel A Adegboyega, Andreas Leithe-Jasper, Mitja Krnel, Yurii Prots, Lev Akselrud, Marcus Schmidt, Ulrich Burkhardt, Jörg Sichelschmidt, Lucia Amidani, Fabio La Mattina, Michael Shatruk, Alexander Shengelaya, Manuel Brando, Eteri Svanidze
{"title":"Unusual Magnetic Order in Eu<sub>11-<i>x</i></sub> Hg<sub>54+<i>x</i></sub>.","authors":"Rachel Nixon, Nazar Zaremba, Samuel A Adegboyega, Andreas Leithe-Jasper, Mitja Krnel, Yurii Prots, Lev Akselrud, Marcus Schmidt, Ulrich Burkhardt, Jörg Sichelschmidt, Lucia Amidani, Fabio La Mattina, Michael Shatruk, Alexander Shengelaya, Manuel Brando, Eteri Svanidze","doi":"10.1021/acsorginorgau.5c00099","DOIUrl":"10.1021/acsorginorgau.5c00099","url":null,"abstract":"<p><p>In solid-state compounds, the valence of europium can sometimes be mixed, which is especially favored in structures with several positions for the europium atoms. In this work, we study the Eu-based intermetallic noncentrosymmetric system Eu<sub>11-<i>x</i></sub> Hg<sub>54+<i>x</i></sub> , which has 65 atoms per unit cell and 4 distinct crystallographic positions for europium and 14 positions for mercury. Our detailed analysis of the magnetism of large single crystals suggests that europium in Eu<sub>11-<i>x</i></sub> Hg<sub>54+<i>x</i></sub> might be present in two valence states, resulting in a fragile magnetic ground state. Due to the cage-like structure with a large distance between the Eu atoms, those atoms are weakly ferromagnetically coupled and Eu<sub>11-<i>x</i></sub> Hg<sub>54+<i>x</i></sub> orders at low temperatures, below <i>T</i> <sub>1</sub> = 5.5 K, with a subsequent spin reorientation at <i>T</i> <sub>2</sub> = 4.3 K. There is no sign of magnetic frustration. Interestingly, the magnetic ordering of the europium substructure results in a magnetization pole reversal with a delicate ferrimagnetic ground state. Additional magnetic phases can be induced by the application of a modest external magnetic field.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"130-138"},"PeriodicalIF":3.3,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879176/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
More than Catalyst Recycling: Tuning Synthetic Photocatalytic Processes via Heterogenization on Silica and Alumina. 超过催化剂回收:通过硅和氧化铝的异质化调整合成光催化过程。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-12-20 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00088
Zacharias Amara, Pierre Zimberlin, Augustin Pirenam Atakpa, Yahya Al Ayi, Maxime Lancel
{"title":"More than Catalyst Recycling: Tuning Synthetic Photocatalytic Processes via Heterogenization on Silica and Alumina.","authors":"Zacharias Amara, Pierre Zimberlin, Augustin Pirenam Atakpa, Yahya Al Ayi, Maxime Lancel","doi":"10.1021/acsorginorgau.5c00088","DOIUrl":"10.1021/acsorginorgau.5c00088","url":null,"abstract":"<p><p>The heterogenization of homogeneous photocatalysts on inert supports such as silica and alumina offers more than improved recyclability. Unlike semiconducting supports such as titanium dioxide, which can alter the photocatalyst behavior through electron injection, insulating oxides preserve the intrinsic photophysical and redox properties of the molecular species. However, such heterogenization is an opportunity to completely modify the physicochemical properties of the surrounding environment, thereby influencing excited-state properties and enhancing reactivity and stability as well as compatibility with green solvents and flow systems. In addition, advanced support design introduces further potential for selectivity or reactivity with gas, although these remain largely underexplored. While silica is widely used due to its tunability and surface area, alumina offers complementary properties but remains less developed. This review highlights the early stage, yet rapidly evolving landscape of heterogenized photocatalysts on silica and alumina, emphasizing the emerging functionalities that extend well beyond catalyst recovery.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"8-22"},"PeriodicalIF":3.3,"publicationDate":"2025-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879186/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
[3 + 2] Cycloadditions of Tertiary Amine N‑Oxides and Azoarenes as a Route to Substituted 1,2,4-Triazolidines. [3 + 2]叔胺N -氧化物和偶氮芳烃环加成取代1,2,4-三唑烷的途径。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-12-05 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00098
Nicholas A Frankos, Malavika S Nair, Aiden M Lane, Megan M Glista, Joshua K Graber, Abbigail E F Black, Trista G L X Newman, Elias R Griffin, Kiera M Luca, Eric J Chartier, David B Heisler, Thomas D Montgomery
{"title":"[3 + 2] Cycloadditions of Tertiary Amine <i>N</i>‑Oxides and Azoarenes as a Route to Substituted 1,2,4-Triazolidines.","authors":"Nicholas A Frankos, Malavika S Nair, Aiden M Lane, Megan M Glista, Joshua K Graber, Abbigail E F Black, Trista G L X Newman, Elias R Griffin, Kiera M Luca, Eric J Chartier, David B Heisler, Thomas D Montgomery","doi":"10.1021/acsorginorgau.5c00098","DOIUrl":"10.1021/acsorginorgau.5c00098","url":null,"abstract":"<p><p>We have developed a synthesis of 29 novel 1,2,4-triazolidines using tertiary amine <i>N</i>-oxides and a wide range of substituted azoarenes. Our method utilizes a base-mediated [3 + 2] cycloaddition, starting from either commercially available or easily accessible precursors to generate triazolidines in yields up to 99%. Density functional theory calculations were performed in parallel to the experimental work to provide insights into the reactivity patterns and the overall mechanism. Finally, preliminary biological data are included on the antibacterial properties of these compounds.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"119-129"},"PeriodicalIF":3.3,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879182/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Novel Nitroxide-Substituted Hydrazone Switch: Experimental and Theoretical Insights into Photoswitching Behavior. 新型氮氧化物取代腙开关:光开关行为的实验和理论见解。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-12-03 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00068
Lucie Kotásková, Ivan Nemec, Radovan Herchel, Vinicius T Santana, Petr Neugebauer
{"title":"Novel Nitroxide-Substituted Hydrazone Switch: Experimental and Theoretical Insights into Photoswitching Behavior.","authors":"Lucie Kotásková, Ivan Nemec, Radovan Herchel, Vinicius T Santana, Petr Neugebauer","doi":"10.1021/acsorginorgau.5c00068","DOIUrl":"10.1021/acsorginorgau.5c00068","url":null,"abstract":"<p><p>Hydrazones are a versatile class of molecular switches with dual responsiveness to both light and pH. To investigate their switching properties, we incorporated a nitroxide moiety, enabling analysis by not only conventional techniques such as <sup>1</sup>H NMR and UV-vis spectroscopy but also EPR spectroscopy, which provides valuable insights into structure and dynamics. A novel nitroxide-substituted hydrazone switch (<b>2</b>) was synthesized and fully characterized. However, initial experiments using <sup>1</sup>H NMR and UV-vis revealed restricted photoisomerization of <b>2</b>. Theoretical studies employing DFT and TD-DFT methods revealed the presence of the D<sub>1</sub> excited state related to π → π* electron transfer of the nitroxide moiety, and D<sub>2</sub> excited state related to π → π* electron transfer within the hydrazone moiety. The latter excitation results in weakening of the CN bond and enables the rotation around the hydrazone bond; however, the internal conversion D<sub>2</sub> → D<sub>1</sub> process is most likely responsible for the quenching of photoisomerization in <b>2</b>. Additionally, pH-induced switching was monitored using UV-vis and EPR spectroscopy, revealing that strong acids such as trifluoroacetic acid had no significant effect on the paramagnetic center.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"64-75"},"PeriodicalIF":3.3,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879170/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143505","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Substituent Effects Govern the Efficiency of Isoxazole Photoisomerization to Carbonyl‑2H‑Azirines. 取代基效应控制异恶唑光异构成羰基- 2H -氮杂化的效率。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-12-01 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00105
Kyra E Jackson, Isabelle Szeto, Leah M Seebald, Samuel G Shepard
{"title":"Substituent Effects Govern the Efficiency of Isoxazole Photoisomerization to Carbonyl‑2<i>H</i>‑Azirines.","authors":"Kyra E Jackson, Isabelle Szeto, Leah M Seebald, Samuel G Shepard","doi":"10.1021/acsorginorgau.5c00105","DOIUrl":"10.1021/acsorginorgau.5c00105","url":null,"abstract":"<p><p>The photoisomerization of isoxazoles is an atom-economical route to carbonyl-2<i>H</i>-azirines, which are valuable in both synthetic and biological applications. However, isolation of the carbonyl-2<i>H</i>-azirine is challenged by reverse photoisomerization back to the isoxazole and irreversible rearrangement to an oxazole. In this work, we demonstrate that substituent selection on 3,5-disubstituted isoxazoles plays a critical role in driving the photochemical isoxazole-azirine equilibrium toward the carbonyl-2<i>H</i>-azirine while avoiding oxazole formation. We find that substituents affect the degree of overlap in the absorption spectra of isoxazole-azirine pairs, where reducing overlap increases the efficiency of photoisomerization. We use time-dependent density functional theory to predict absorption spectra for isomer pairs with varied 3,5-disubstituents, identifying <i>tert</i>-butyl- and trifluoromethyl-substituted 5-aminoisoxazoles as promising structures. We then tested these predictions experimentally, revealing efficient formation of carbonyl-2<i>H</i>-azirines in high yields with minimal oxazole formation. This is in contrast to a phenyl-substituted 5-aminoisoxazole, which was found to readily form oxazoles, precluding isolation of the carbonyl-2<i>H</i>-azirine. These results demonstrate the utility of substituent-driven design for tuning photoisomerization equilibria and provide an atom-economical option for generating carbonyl-2<i>H</i>-azirines on synthetically useful scales.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"41-46"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879163/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143555","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The "Missing Link", Allostery and SynergismHosting of Metal Cations by Regular and Partial Cone Calix[4]arene Isomers. “缺失的一环”、变构和协同作用金属阳离子在规整和部分锥杯[4]芳烃异构体中的吸附。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-11-12 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00095
Matija Modrušan, Nikola Cindro, Marija Cvetnić, Andrea Usenik, Slavica Petrović, Jakov Borovec, Katarina Leko, Karla Kukina Gradečak, Vladimir Stilinović, Gordan Horvat, Tomica Hrenar, Josip Požar, Vladislav Tomišić
{"title":"The \"Missing Link\", Allostery and SynergismHosting of Metal Cations by Regular and Partial <i>Cone</i> Calix[4]arene Isomers.","authors":"Matija Modrušan, Nikola Cindro, Marija Cvetnić, Andrea Usenik, Slavica Petrović, Jakov Borovec, Katarina Leko, Karla Kukina Gradečak, Vladimir Stilinović, Gordan Horvat, Tomica Hrenar, Josip Požar, Vladislav Tomišić","doi":"10.1021/acsorginorgau.5c00095","DOIUrl":"10.1021/acsorginorgau.5c00095","url":null,"abstract":"<p><p>The influence of the tetra-<i>O</i>-2-oxopropyl-substituted calix-[4]-arene conformation on its binding affinity toward first- and second-group metal cations, as well as on the solvent molecule (acetonitrile or methanol) inclusion in the calixarene hydrophobic cavity, was investigated experimentally and computationally. Misorientation of one monomeric subunit in the partial <i>cone</i> ligand (<b>L</b> <sub><b>p</b></sub> ) led to incomplete cation desolvation and significantly reduced its cation-binding ability compared to the regular <i>cone</i> isomer (<b>L</b> <sub><b>c</b></sub> ). Aromatic ring inversion also precluded solvent inclusion in the calixarene <i>basket</i> of both free and complexed <b>L</b> <sub><b>p</b></sub> (in contrast to <b>L</b> <sub><b>c</b></sub> ), which considerably affected the complex stabilities and highlighted the pronounced cooperative allosteric effect of this process on the cation binding. Comprehensive structural and energetic studies, carried out by classical molecular dynamics simulations and quantum chemical calculations, showed that inclusion of acetonitrile within the complexes was favored over methanol, whereby the nitrile group of the solvent coordinated the second-group cations. Conversely, the methyl group of included acetonitrile or methanol molecule faced the alkali metal cations in the corresponding adducts. Molecular and crystal structures of free <b>L</b> <sub><b>p</b></sub> , as well as sodium, calcium, and barium complexes of <b>L</b> <sub><b>c</b></sub> with included acetonitrile, were determined by single-crystal X-ray diffraction. The orientations of solvent molecules within the calixarene cavity in the solid state closely matched computational predictions, further supporting conclusions drawn from the experimental data. Overall, this work presents a particularly detailed account of the thermodynamic and structural aspects of chelate, macrocyclic, and medium effects on the cation-hosting processes, providing valuable insights into the driving forces governing supramolecular recognition in solution.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"88-103"},"PeriodicalIF":3.3,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879178/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143532","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Rotational Behavior in Piano Stool Ru(II) Complexes with Bulky-Substituted Cyclopentadienyl Ligands. 含大取代环戊二烯配体的钢琴凳Ru(II)配合物的旋转行为。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-11-06 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00100
Naoki Ito, Toshio Nishino, Jérôme Cuny, Shohei Katao, Kazuma Yasuhara, Gwénaël Rapenne
{"title":"Rotational Behavior in Piano Stool Ru(II) Complexes with Bulky-Substituted Cyclopentadienyl Ligands.","authors":"Naoki Ito, Toshio Nishino, Jérôme Cuny, Shohei Katao, Kazuma Yasuhara, Gwénaël Rapenne","doi":"10.1021/acsorginorgau.5c00100","DOIUrl":"10.1021/acsorginorgau.5c00100","url":null,"abstract":"<p><p>In this study, we designed and synthesized a series of novel piano stool ruthenium complexes featuring bulky substituents on the cyclopentadienyl (Cp) ligand to investigate how the substituent structure affects rotational behavior around the Cp-Ru bond. Substituents, including <i>m</i>-xylyl, mesityl, and 9-anthracenyl groups, were introduced to create steric hindrance with the tripodal ligand to increase the rotational barrier. NMR spectroscopy revealed that the Cp-Ru bond in the complex with the <i>m</i>-xylyl group rotated faster than the NMR time scale, whereas complexes bearing mesityl and 9-anthracenyl groups exhibited slower rotation. Variable-temperature NMR measurements and line shape fitting analysis showed that the activation free energy (Δ<i>G</i> <sup>⧧</sup>) required for the Cp ligand rotation by overcoming the steric hindrance between the substituent and tripodal ligand was significantly higher for the mesityl (69.5 kJ mol<sup>-1</sup>) and 9-anthracenyl (67.8 kJ mol<sup>-1</sup>) complexes compared to the previously reported pentaphenyl Cp complex (18.9 kJ mol<sup>-1</sup>). The results indicate that the activation enthalpy is the primary contributor to the overall activation energy, suggesting that the bulky substituents increase the rotational barrier by occupying the spatial gap between the pyrazole rings of the tripodal ligand. This is confirmed by theoretical calculations and the characterization of the minimum energy paths and transition states for each species. These findings offer valuable guidance for the molecular design of STM-operable molecular motors that can function at or near ambient temperature instead of the typical extremely low-temperature conditions necessary to suppress random molecular motion caused by thermal excitation.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"139-148"},"PeriodicalIF":3.3,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12879173/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The Combined Role of Silanols and Oxidative Stress in Determining Engineered Stone Dust Toxicity. 硅烷醇和氧化应激在决定工程石尘毒性中的联合作用。
IF 3.3
ACS Organic & Inorganic Au Pub Date : 2025-11-05 eCollection Date: 2026-02-04 DOI: 10.1021/acsorginorgau.5c00089
Cristina Pavan, Marianna Fimiani, Stefania Cananà, Aleandro Diana, Matteo Marafante, Stefano Bertinetti, Guillermo Escolano-Casado, Lorenzo Mino, Dino Pisaniello, Riccardo Leinardi, Maura Tomatis, Francesco Turci
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