ACS Organic & Inorganic Au最新文献

{"title":"The Acidity of Weak NH Acids: Expanding the pKa Scale in Acetonitrile","authors":"Märt Lõkov*,&nbsp;Carmen Kesküla,&nbsp;Sofja Tshepelevitsh,&nbsp;Marta-Lisette Pikma,&nbsp;Jaan Saame,&nbsp;Dmitri Trubitsõn,&nbsp;Tõnis Kanger and Ivo Leito,&nbsp;","doi":"10.1021/acsorginorgau.4c0009510.1021/acsorginorgau.4c00095","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00095https://doi.org/10.1021/acsorginorgau.4c00095","url":null,"abstract":"<p >Nitrogen heterocycles and aromatic amines are well-known and widely used compounds that are usually not seen as acids, although in organic solvents like acetonitrile (MeCN) or dimethyl sulfoxide (DMSO) their acidic properties can be observed. In this work, the acidities (p<i>K</i>_a values) of 37 such weak NH acids were determined in acetonitrile and presented together with computational gas-phase acidities and literature p<i>K</i>_a values in DMSO. In the course of the work the weakest acids range (from p<i>K</i>_a 29 upward) of the MeCN acidity scale has been revised and expanded to around 33.5 by adding 31 compounds in that specific region and the span of experimental p<i>K</i>_a values in MeCN is now more than 30 orders of magnitude. The relations between the structure and acidity of a selection of the studied compounds have been investigated in MeCN and DMSO. The measured p<i>K</i>_a values in MeCN and the gathered p<i>K</i>_a values in DMSO were used for a correlation analysis between the two solvents and for assessing the quality of p<i>K</i>_a conversion equations. A number of p<i>K</i>_a values have been predicted in MeCN from p<i>K</i>_a values in DMSO via the correlation analysis and p<i>K</i>_a conversion equations.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"144–155 144–155"},"PeriodicalIF":3.3,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00095","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143746039","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}

{"title":"When Pore Met Semi: Charting the Rise of Porous Metal Halide Semiconductors","authors":"Ali Azmy,&nbsp;Alissa Brooke Anderson,&nbsp;Mina Bagherifard,&nbsp;Neelam Tariq,&nbsp;Kamal E. S. Nassar and Ioannis Spanopoulos*,&nbsp;","doi":"10.1021/acsorginorgau.4c0009310.1021/acsorginorgau.4c00093","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00093https://doi.org/10.1021/acsorginorgau.4c00093","url":null,"abstract":"<p >Metal halide semiconductors (MHS) are a versatile class of materials with fully customizable mechanical and optoelectronic properties that have proven to be prominent candidates in numerous impactful applications. Finding a way to generate porosity in MHS would bestow upon them an additional node in property engineering, thus allowing them to be utilized in uncharted technologies. Motivated by this promise, we developed a general strategy to render the MHS porous. We employed molecular cages as structure-directing agents and countercations, which fostered a new family of materials: porous metal halide semiconductors (PMHS). The presence of molecular cages gave rise to ultramicroporous structures imposed by the organic part cavities and a record water stability performance of 27 months so far. In this Perspective, we discuss the principles and promises of PMHS, which combine the merits of porous and electronic compounds.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"87–96 87–96"},"PeriodicalIF":3.3,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00093","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745969","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}

{"title":"Celebrating 5 Years of the ACS Au Journal Family","authors":"Paul D. Goring,&nbsp;Amelia Newman,&nbsp;Christopher W. Jones* and Shelley D. Minteer*,&nbsp;","doi":"10.1021/acsorginorgau.5c0001510.1021/acsorginorgau.5c00015","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00015https://doi.org/10.1021/acsorginorgau.5c00015","url":null,"abstract":"","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"84–86 84–86"},"PeriodicalIF":3.3,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00015","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745926","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}

{"title":"One-Pot NIS-Promoted Cyclization/Palladium-Catalyzed Carbonylation for the Selective Synthesis of HFIP Ester-Containing Indenes and Thiochromenes","authors":"Pengfei Ji,&nbsp;Xing-Feng Pan,&nbsp;Xinxin Qi* and Xiao-Feng Wu*,&nbsp;","doi":"10.1021/acsorginorgau.5c0000510.1021/acsorginorgau.5c00005","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00005https://doi.org/10.1021/acsorginorgau.5c00005","url":null,"abstract":"<p >Practical and atom-economic procedures for the selective synthesis of HFIP ester-containing indenes/thiochromenes from the same propargylic thioethers and HFIP have been developed via one-pot NIS-promoted cyclization/palladium-catalyzed carbonylation. Solvent plays an important role in this transformation, and the reactions proceed selectively and efficiently to afford a variety of HFIP ester-containing indenes and thiochromenes in moderate to excellent yields. In addition, the use of formic acid as the CO source could avoid manipulation of toxic CO gas.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"156–163 156–163"},"PeriodicalIF":3.3,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00005","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745874","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}

{"title":"Rearrangement Cascade Initiated by Nucleophilic Benzyne Attack on 3,6-Di(2-pyridyl)-1,2-diazines","authors":"Johannes Schöntag,&nbsp;Theresa Hettiger,&nbsp;William Roberts,&nbsp;Marcus Scheele,&nbsp;Markus Ströbele and Holger F. Bettinger*,&nbsp;","doi":"10.1021/acsorginorgau.4c0007010.1021/acsorginorgau.4c00070","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00070https://doi.org/10.1021/acsorginorgau.4c00070","url":null,"abstract":"<p >Aryne intermediates in synthetic organic chemistry offer versatile routes to complex heterocyclic structures that are valuable in pharmaceuticals and materials science. We present a one-step aryne-mediated reaction to synthesize pyrido[1,2-<i>a</i>]indoles interconnected through vinylene or 1,2-phenylene linkers to pyridotriazoles using 2-pyridyl-substituted pyridazines and phthalazines as confirmed via single-crystal X-ray crystallography and NMR spectroscopy. This unexpected rearrangement proceeds under mild conditions. Considering that five bonds are broken and three new bonds are formed in the reaction between 3,6-di-2-pyridyl-1,2,4,5-tetrazine and benzyne, the yield of 16% is fair. Electron-rich substituents on aryne precursors destabilized the products, while electron-deficient substituents offered some stability improvements. DFT studies could reveal the mechanism of this rearrangement.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"97–104 97–104"},"PeriodicalIF":3.3,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00070","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745973","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}

{"title":"N-Heterocyclic Carbene-Borane Adducts with Chiral (R)-Chloroethyl and Vinyl Substituents","authors":"Germán Rodríguez-López,&nbsp;Tayde O. Villaseñor-Granados,&nbsp;Sonia Sánchez-Ruiz,&nbsp;Adriana Esparza-Ruiz* and Angelina Flores-Parra*,&nbsp;","doi":"10.1021/acsorginorgau.4c0008810.1021/acsorginorgau.4c00088","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00088https://doi.org/10.1021/acsorginorgau.4c00088","url":null,"abstract":"<p >This research provides how chiral imidazolium salts {1,3-bis[1′-chloro-1′-phenylpropan-2′-yl]-imidazolium} (<b>1a</b>) and enantiopure {1,3-bis[(<i>R</i>)-1-chlorobutan-2-yl]-imidazolium} [<b>1b</b>] can be utilized in diverse synthetic pathways to obtain new carbene-borane adducts (<b>2a</b>–<b>2d</b>): {1,3-bis[1′-chloro-1′-phenylpropan-2′-yl]-imidazolyl-2-ylidene-borane} (<b>2a</b>), {1,3-bis[(<i>Z</i>)-1′-phenylpropen-2′-yl]-imidazolyl-2-ylidene-borane} (<b>2b</b>), {1,3-bis[(<i>R</i>)-1-chlorobutan-2-yl]-imidazolyl-2-ylidene-borane} (<b>2c</b>), and {1,3-bis[but-1-en-2-yl]-imidazolyl-2-ylidene-borane} (<b>2d</b>). The carbene-borane adducts were synthesized and characterized by ¹³C, ¹H, and ¹¹B nuclear magnetic resonance spectroscopy and time-of-flight mass spectrometry. The X-ray crystal analyses of compounds <b>2a</b> and <b>2b</b> were performed, and to understand the structure and interactions of <b>2a</b>, a computational study was carried out. The effect of <i>N</i>-substituents in the NHC-borane adducts was clearly observed in the C–B bond lengths obtained by single-crystal X-ray diffraction, where the C–B bond is longer for adducts with <i>N</i>-(<i>R</i>)-chloroethyl substituents than for vinyl substituents. The analysis of the reduced density gradient and the bond critical point calculations of <b>2a</b> showed intramolecular proton–hydride and Cl···N interactions. These chiral imidazolium salts could have applicability in the development of new materials and possibly in pharmaceutical research.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"136–143 136–143"},"PeriodicalIF":3.3,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00088","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745972","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}

{"title":"Strategic Methodologies for Efficient Synthesis of Imidazo[1,5-a]pyridine and Benzazepine Analogs via the Unique Ritter-Type Reaction","authors":"Gunniga Tanomsiri,&nbsp;Suthimon Boonmee,&nbsp;Nattawadee Chaisan,&nbsp;Jumreang Tummatorn*,&nbsp;Charnsak Thongsornkleeb and Somsak Ruchirawat,&nbsp;","doi":"10.1021/acsorginorgau.4c0007510.1021/acsorginorgau.4c00075","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00075https://doi.org/10.1021/acsorginorgau.4c00075","url":null,"abstract":"<p >We have developed novel approaches for synthesizing imidazo[1,5-<i>a</i>]pyridine and benzazepine analogs through a Ritter-type reaction. These methods utilize bismuth(III) trifluoromethanesulfonate (Bi(OTf)₃), an efficient catalyst for converting benzylic alcohol into benzylic cations, in combination with <i>para</i>-toluenesulfonic acid (<i>p</i>-TsOH·H₂O). The procedures offer a wide substrate scope and deliver the desired products in yields ranging from moderate to excellent.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"117–135 117–135"},"PeriodicalIF":3.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745868","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}

{"title":"Single-Ion-Conducting Polymer Electrolytes for Rechargeable Alkaline Ag-Zn Batteries.","authors":"Hunter O Ford, Brian L Chaloux, Nishani K Jayakody, Christopher A Klug, Eric G Ruzicka, Meghanne Tighe, Ryan H DeBlock, Jeffrey W Long, Debra R Rolison, Megan Bourg Sassin","doi":"10.1021/acsorginorgau.4c00053","DOIUrl":"10.1021/acsorginorgau.4c00053","url":null,"abstract":"<p><p>Recently, we reported on the synthesis and performance of a cross-linked single-anion-conducting solid-state electrolyte (SSE) based on quaternized poly(dimethylaminomethylstyrene) (pDMAMS⁺) via initiated chemical vapor deposition (iCVD). In the homopolymer pDMAMS⁺-based SSE, the cross-linking occurs at the positively charged ammonium cation sites, hindering ion transport and conductivity. To improve ionic conductivity, we now report on a copolymer system, comprising DMAMS and divinylbenzene (DVB). Incorporating DVB moves the cross-links to the polymer backbone leaving the quaternary ammonium cation and its paired anion with maximal dynamic freedom. We evaluate the structure-transport relationships of a series of p[DVB-DMAMS] copolymers with varying DVB content using electrochemical impedance spectroscopy, nuclear magnetic resonance spectroscopy, and small- and wide-angle X-ray scattering. Our best composition containing 2.5 wt % DVB provides 1 mS cm^-1 single-ion OH^- conductivity under hydrated conditions, a significant improvement over the 0.01 mS cm^-1 of the hydrated homopolymer pDMAMS⁺ SSE. All copolymer compositions support Zn-ZnO and Ag-Zn electrochemical reduction-oxidation (redox) chemistry, which demonstrates the feasibility of a Ag-Zn battery using an alkaline single-ion-conducting SSE. Galvanostatic cycling shows some transport of Ag through the polymer electrolyte, however the deleterious effects of Ag migration can be partially mitigated by transitioning from a two-dimensional (2D) planar electrode to a 3D sponge electrode. With these promising results, the foundation is laid for using single-anion-conducting SSEs within alkaline Zn batteries.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"37-46"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11803467/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143383467","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}

{"title":"Hydrogen Oxidation by Bioinspired Models of [FeFe]-Hydrogenase","authors":"Abhijit Nayek,&nbsp;Rabin Kumar Poria,&nbsp;Md Estak Ahmed,&nbsp;Suman Patra,&nbsp;Somdatta Ghosh Dey* and Abhishek Dey*,&nbsp;","doi":"10.1021/acsorginorgau.4c0007310.1021/acsorginorgau.4c00073","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00073https://doi.org/10.1021/acsorginorgau.4c00073","url":null,"abstract":"<p >Synthetic azadithiolate-bridged diiron clusters serve as structural analogues of the active site of [FeFe]-hydrogenases. Recently, an <i>o-</i>alkyl substitution of aniline-based azadithiolate bridge allowed these synthetic models to both oxidize H₂ and reduce H⁺, i.e., bidirectional catalysis. Hydrogen oxidation by synthetic analogues of hydrogenases is rare, and even rarer is the ability of diiron hexacarbonyls to oxidize H₂. A series of synthetic azadithiolate-bridged biomimetic diiron hexacarbonyl complexes are synthesized where the substitution in the <i>para</i> position of the <i>ortho-</i>methyl aniline in the azadithiolate bridge is systematically varied between electron-withdrawing and electron-donating groups to understand factors that control H₂ oxidation by diiron hexacarbonyl analogues of [FeFe]-hydrogenases. The results show that the substituents in the <i>para</i> position of the <i>ortho-</i>ethyl aniline affect the electronic structure of the azadithiolate bridge as well as that of the diiron cluster. The electron-withdrawing −NO₂ substituent results in faster H₂ oxidation relative to that of a −OCH₃ substituent.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 2","pages":"105–116 105–116"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745870","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}

{"title":"Single-Ion-Conducting Polymer Electrolytes for Rechargeable Alkaline Ag–Zn Batteries","authors":"Hunter O. Ford,&nbsp;Brian L. Chaloux,&nbsp;Nishani K. Jayakody,&nbsp;Christopher A. Klug,&nbsp;Eric G. Ruzicka,&nbsp;Meghanne Tighe,&nbsp;Ryan H. DeBlock,&nbsp;Jeffrey W. Long,&nbsp;Debra R. Rolison and Megan Bourg Sassin*,&nbsp;","doi":"10.1021/acsorginorgau.4c0005310.1021/acsorginorgau.4c00053","DOIUrl":"https://doi.org/10.1021/acsorginorgau.4c00053https://doi.org/10.1021/acsorginorgau.4c00053","url":null,"abstract":"<p >Recently, we reported on the synthesis and performance of a cross-linked single-anion-conducting solid-state electrolyte (SSE) based on quaternized poly(dimethylaminomethylstyrene) (pDMAMS⁺) via initiated chemical vapor deposition (iCVD). In the homopolymer pDMAMS⁺-based SSE, the cross-linking occurs at the positively charged ammonium cation sites, hindering ion transport and conductivity. To improve ionic conductivity, we now report on a copolymer system, comprising DMAMS and divinylbenzene (DVB). Incorporating DVB moves the cross-links to the polymer backbone leaving the quaternary ammonium cation and its paired anion with maximal dynamic freedom. We evaluate the structure–transport relationships of a series of p[DVB-DMAMS] copolymers with varying DVB content using electrochemical impedance spectroscopy, nuclear magnetic resonance spectroscopy, and small- and wide-angle X-ray scattering. Our best composition containing 2.5 wt % DVB provides 1 mS cm^–1 single-ion OH^– conductivity under hydrated conditions, a significant improvement over the 0.01 mS cm^–1 of the hydrated homopolymer pDMAMS⁺ SSE. All copolymer compositions support Zn–ZnO and Ag–Zn electrochemical reduction–oxidation (redox) chemistry, which demonstrates the feasibility of a Ag–Zn battery using an alkaline single-ion-conducting SSE. Galvanostatic cycling shows some transport of Ag through the polymer electrolyte, however the deleterious effects of Ag migration can be partially mitigated by transitioning from a two-dimensional (2D) planar electrode to a 3D sponge electrode. With these promising results, the foundation is laid for using single-anion-conducting SSEs within alkaline Zn batteries.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 1","pages":"37–46 37–46"},"PeriodicalIF":3.3,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.4c00053","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126441","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}