ACS Organic & Inorganic Au最新文献

{"title":"Electrochemical Explorations in Organic and Inorganic Chemistry.","authors":"Shelley Minteer","doi":"10.1021/acsorginorgau.5c00044","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00044","url":null,"abstract":"","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"164-165"},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12142434/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144249929","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":"Electrochemical Explorations in Organic and Inorganic Chemistry","authors":"Shelley Minteer*, ","doi":"10.1021/acsorginorgau.5c0004410.1021/acsorginorgau.5c00044","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00044https://doi.org/10.1021/acsorginorgau.5c00044","url":null,"abstract":"","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"164–165 164–165"},"PeriodicalIF":3.3,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00044","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202554","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":"<i>N</i>‑Heterocyclic Carbene-Based Group 4 Catalysts for the Terpolymerization of Cyclohexene Oxide and Cyclic Anhydrides with CO₂.","authors":"Lakshmi Suresh, Kathrin Zwettler, Karl W Törnroos, William Le, Benoît Marcolini, Gilles Frache, Erwan Le Roux","doi":"10.1021/acsorginorgau.5c00002","DOIUrl":"10.1021/acsorginorgau.5c00002","url":null,"abstract":"<p><p>A series of bis-phenolate saturated <i>N</i>-heterocyclic carbene (NHC) group 4 complexes ([κ³-O,C,O]-NHC)-M-(O<i>i</i>Pr)-Cl-(THF) (M = Ti, <b>1</b>; Zr, <b>2</b>; Hf, <b>3</b>) in the presence of [PPN]Cl as cocatalyst were investigated and showed high activity in the tandem terpolymerization of phthalic anhydride (PA), cyclohexene oxide (CHO) with CO₂. The resultant terpolymers revealed a diblock pattern leading selectively to poly-(ester-<i>b</i>-carbonate). Subsequently, other titanium complexes ([κ³-O,C,O]-NHC)-TiX₂ bearing various coligands (X = Cl, <b>4</b>; O<i>i</i>Pr, <b>5</b>; OAc, <b>6</b>; OAc^F, <b>7</b>) also displayed high activity with a turnover frequency (TOF) up to 460 h^-1 that is comparable to <b>1</b>. Using the same tandem approach, the nature of terpolymers was modulated with other mono- and tricyclic anhydrides alongside CHO with CO₂. Intrigued by the high rates of PA conversion observed experimentally in terpolymerization, complexes <b>1</b>-<b>3</b> as well as benzannulated and unsaturated NHC analogues of complex <b>1</b> were investigated as a stand-alone reaction for the copolymerization of PA and CHO. Complex <b>1</b>/[PPN]Cl displayed excellent catalytic activity (TOF ∼ 1600 h^-1) and high selectivity (≥99%) toward polyesters comparable to other highly active heteronuclear (Al/K and Fe/K) catalysts and binary (salen)-MX systems. Kinetic studies performed on complexes <b>1</b> and <b>3</b> determined activation barriers (<i>E</i> _a) consistent with the observed catalytic trend, <i>i.e</i>., <i>E</i> _a: Ti < Hf.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"171-180"},"PeriodicalIF":3.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12142441/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144249928","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-Based Group 4 Catalysts for the Terpolymerization of Cyclohexene Oxide and Cyclic Anhydrides with CO2","authors":"Lakshmi Suresh,&nbsp;Kathrin Zwettler,&nbsp;Karl W. Törnroos,&nbsp;William Le,&nbsp;Benoît Marcolini,&nbsp;Gilles Frache and Erwan Le Roux*,&nbsp;","doi":"10.1021/acsorginorgau.5c0000210.1021/acsorginorgau.5c00002","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00002https://doi.org/10.1021/acsorginorgau.5c00002","url":null,"abstract":"<p >A series of bis-phenolate saturated <i>N</i>-heterocyclic carbene (NHC) group 4 complexes ([κ³-O,C,O]-NHC)M(O<i>i</i>Pr)Cl(THF) (M = Ti, <b>1</b>; Zr, <b>2</b>; Hf, <b>3</b>) in the presence of [PPN]Cl as cocatalyst were investigated and showed high activity in the tandem terpolymerization of phthalic anhydride (PA), cyclohexene oxide (CHO) with CO₂. The resultant terpolymers revealed a diblock pattern leading selectively to poly(ester-<i>b</i>-carbonate). Subsequently, other titanium complexes ([κ³-O,C,O]-NHC)TiX₂ bearing various coligands (X = Cl, <b>4</b>; O<i>i</i>Pr, <b>5</b>; OAc, <b>6</b>; OAc^F, <b>7</b>) also displayed high activity with a turnover frequency (TOF) up to 460 h^–1 that is comparable to <b>1</b>. Using the same tandem approach, the nature of terpolymers was modulated with other mono- and tricyclic anhydrides alongside CHO with CO₂. Intrigued by the high rates of PA conversion observed experimentally in terpolymerization, complexes <b>1</b>–<b>3</b> as well as benzannulated and unsaturated NHC analogues of complex <b>1</b> were investigated as a stand-alone reaction for the copolymerization of PA and CHO. Complex <b>1</b>/[PPN]Cl displayed excellent catalytic activity (TOF ∼ 1600 h^–1) and high selectivity (≥99%) toward polyesters comparable to other highly active heteronuclear (Al/K and Fe/K) catalysts and binary (salen)MX systems. Kinetic studies performed on complexes <b>1</b> and <b>3</b> determined activation barriers (<i>E</i>_a) consistent with the observed catalytic trend, <i>i.e</i>., <i>E</i>_a: Ti &lt; Hf.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"171–180 171–180"},"PeriodicalIF":3.3,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00002","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202775","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":"Red Light and Supersilane: A Novel Pathway for Hydrofunctionalizations and Giese Reactions","authors":"Aakanksha Gurawa,&nbsp;Marc Taillefer and Alexis Prieto*,&nbsp;","doi":"10.1021/acsorginorgau.5c0003210.1021/acsorginorgau.5c00032","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00032https://doi.org/10.1021/acsorginorgau.5c00032","url":null,"abstract":"<p >Herein, we describe the photoredox activation of silanes under deep-red irradiation with or without osmium-based photocatalysts to generate silyl radicals. These radicals were further employed for achieving various reactivities previously unexplored in the red-light spectral region, such as hydrosilylation, hydrosulfonylation, and Giese reaction. Overall, the developed deep-red protocols allow for the preparation of a diverse array of high-value molecules.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"221–227 221–227"},"PeriodicalIF":3.3,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00032","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202717","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":"Red Light and Supersilane: A Novel Pathway for Hydrofunctionalizations and Giese Reactions.","authors":"Aakanksha Gurawa, Marc Taillefer, Alexis Prieto","doi":"10.1021/acsorginorgau.5c00032","DOIUrl":"10.1021/acsorginorgau.5c00032","url":null,"abstract":"<p><p>Herein, we describe the photoredox activation of silanes under deep-red irradiation with or without osmium-based photocatalysts to generate silyl radicals. These radicals were further employed for achieving various reactivities previously unexplored in the red-light spectral region, such as hydrosilylation, hydrosulfonylation, and Giese reaction. Overall, the developed deep-red protocols allow for the preparation of a diverse array of high-value molecules.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"221-227"},"PeriodicalIF":3.3,"publicationDate":"2025-05-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12142440/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144249943","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":"Physicochemical Properties of Tin and Neodymium Co-Doped Phosphate Glasses: Tuning the UV-Excited Nd3+ NIR Emission via Sn2+","authors":"José A. Jiménez*,&nbsp;Dugan Hayes,&nbsp;Solaleh Farnia and Michael Vautier,&nbsp;","doi":"10.1021/acsorginorgau.5c0000610.1021/acsorginorgau.5c00006","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00006https://doi.org/10.1021/acsorginorgau.5c00006","url":null,"abstract":"<p >This work reports on various physicochemical properties and energy conversion processes in phosphate glasses containing Sn²⁺ and Nd³⁺ ions of interest for luminescence-based applications. The glasses were prepared by melting with 50P₂O₅-(49 – <i>x</i>)BaO-1Nd₂O₃-<i>x</i>SnO (<i>x</i> = 0, 1.0, 3.0, 5.0, 7.0, and 9.0 mol %) nominal compositions and characterized by X-ray diffraction, ¹¹⁹Sn Mössbauer spectroscopy, density and related physical properties, Raman spectroscopy, differential scanning calorimetry, dilatometry, optical absorption, and photoluminescence (PL) spectroscopy. X-ray diffraction confirmed the noncrystalline nature of the glasses. The ¹¹⁹Sn Mössbauer evaluation allowed for estimating the relative amounts of Sn²⁺ and Sn⁴⁺ in the glasses, which showed that Sn²⁺ occurrence was favored. The densities showed variations without definite trends; additional physical parameters were then determined such as Sn²⁺-Nd³⁺ distances based on ¹¹⁹Sn Mössbauer results. The characterization by Raman spectroscopy showed no significant structural variation was induced as SnO replaced BaO. The thermal properties of the codoped glasses assessed were however found to be impacted mostly by Sn²⁺ at high nominal SnO contents. Absorption spectra supported consistent occurrence of Nd³⁺ ions among the codoped glasses. The PL evaluation showed that exciting Sn²⁺ centers in the UV (e.g., near 290 nm) results in near-infrared emission from Nd³⁺, which was maximized for SnO added at 5 mol %. The visible PL data were consistent with the presence of Sn²⁺ in the glasses and showed dips in the emission spectra, indicating the energy transfer to Nd³⁺ ions. The Nd³⁺ decay times were however similar among the different samples.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"194–204 194–204"},"PeriodicalIF":3.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00006","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202756","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":"Physicochemical Properties of Tin and Neodymium Co-Doped Phosphate Glasses: Tuning the UV-Excited Nd³⁺ NIR Emission via Sn².","authors":"José A Jiménez, Dugan Hayes, Solaleh Farnia, Michael Vautier","doi":"10.1021/acsorginorgau.5c00006","DOIUrl":"10.1021/acsorginorgau.5c00006","url":null,"abstract":"<p><p>This work reports on various physicochemical properties and energy conversion processes in phosphate glasses containing Sn²⁺ and Nd³⁺ ions of interest for luminescence-based applications. The glasses were prepared by melting with 50P₂O₅-(49 - <i>x</i>)-BaO-1Nd₂O₃-<i>x</i>SnO (<i>x</i> = 0, 1.0, 3.0, 5.0, 7.0, and 9.0 mol %) nominal compositions and characterized by X-ray diffraction, ¹¹⁹Sn Mössbauer spectroscopy, density and related physical properties, Raman spectroscopy, differential scanning calorimetry, dilatometry, optical absorption, and photoluminescence (PL) spectroscopy. X-ray diffraction confirmed the noncrystalline nature of the glasses. The ¹¹⁹Sn Mössbauer evaluation allowed for estimating the relative amounts of Sn²⁺ and Sn⁴⁺ in the glasses, which showed that Sn²⁺ occurrence was favored. The densities showed variations without definite trends; additional physical parameters were then determined such as Sn²⁺-Nd³⁺ distances based on ¹¹⁹Sn Mössbauer results. The characterization by Raman spectroscopy showed no significant structural variation was induced as SnO replaced BaO. The thermal properties of the codoped glasses assessed were however found to be impacted mostly by Sn²⁺ at high nominal SnO contents. Absorption spectra supported consistent occurrence of Nd³⁺ ions among the codoped glasses. The PL evaluation showed that exciting Sn²⁺ centers in the UV (e.g., near 290 nm) results in near-infrared emission from Nd³⁺, which was maximized for SnO added at 5 mol %. The visible PL data were consistent with the presence of Sn²⁺ in the glasses and showed dips in the emission spectra, indicating the energy transfer to Nd³⁺ ions. The Nd³⁺ decay times were however similar among the different samples.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"194-204"},"PeriodicalIF":3.3,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12142439/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144249942","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":"Structural Analysis of Tin-Substituted High-Entropy Li-Garnet Electrolytes for Solid-State Batteries.","authors":"Benjamin Zimmermann, Till Fuchs, Johannes Westphal, Jürgen Janek, Maren Lepple","doi":"10.1021/acsorginorgau.5c00021","DOIUrl":"10.1021/acsorginorgau.5c00021","url":null,"abstract":"<p><p>Lithium garnets offer promising structural and electrochemical properties and could be used in all solid-state lithium batteries replacing liquid electrolytes. They can operate in a wide electrochemical voltage window and show high ionic conductivities (>10^-4 S cm^-1). The best-studied lithium garnet is Li₇La₃Zr₂O₁₂ (LLZO), which is known to undergo a transition from an ordered, tetragonal form to a disordered cubic modification at elevated temperatures. This is crucial, as the cubic modification offers about 2 orders of magnitude higher ionic conductivities. Applying the high-entropy concept to this material facilitates the stabilization of the cubic structure at ambient conditions. In this work, four different lithium garnet compositions based on Li₆La₃Zr_0.5Nb_0.5Ta_0.5Hf_0.5O₁₂ have been synthesized by mixing Zr⁴⁺, Nb⁵⁺, Ta⁵⁺, and Hf⁴⁺ by Sn⁴⁺, respectively, using two different solid-state approaches. They have been characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, and impedance spectroscopy to analyze the influence of synthesis parameters and composition on phase purity, elemental distribution, and ionic conductivity. It was found that combining calcination and sintering into one process yields a higher density and ionic conductivity than splitting it into two with intermediate regrinding of the material. Impedance data indicate an increase in ionic conductivity when substituting pentavalent ions for tetravalent ones due to the resulting higher concentration of mobile charge carriers in the structure, compared to Li₆La₃Zr_0.5Nb_0.5Ta_0.5Hf_0.5O₁₂.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"211-220"},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12142435/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144249944","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":"Structural Analysis of Tin-Substituted High-Entropy Li-Garnet Electrolytes for Solid-State Batteries","authors":"Benjamin Zimmermann,&nbsp;Till Fuchs,&nbsp;Johannes Westphal,&nbsp;Jürgen Janek and Maren Lepple*,&nbsp;","doi":"10.1021/acsorginorgau.5c0002110.1021/acsorginorgau.5c00021","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00021https://doi.org/10.1021/acsorginorgau.5c00021","url":null,"abstract":"<p >Lithium garnets offer promising structural and electrochemical properties and could be used in all solid-state lithium batteries replacing liquid electrolytes. They can operate in a wide electrochemical voltage window and show high ionic conductivities (&gt;10^–4 S cm^–1). The best-studied lithium garnet is Li₇La₃Zr₂O₁₂ (LLZO), which is known to undergo a transition from an ordered, tetragonal form to a disordered cubic modification at elevated temperatures. This is crucial, as the cubic modification offers about 2 orders of magnitude higher ionic conductivities. Applying the high-entropy concept to this material facilitates the stabilization of the cubic structure at ambient conditions. In this work, four different lithium garnet compositions based on Li₆La₃Zr_0.5Nb_0.5Ta_0.5Hf_0.5O₁₂ have been synthesized by mixing Zr⁴⁺, Nb⁵⁺, Ta⁵⁺, and Hf⁴⁺ by Sn⁴⁺, respectively, using two different solid-state approaches. They have been characterized by X-ray diffraction, energy-dispersive X-ray spectroscopy, and impedance spectroscopy to analyze the influence of synthesis parameters and composition on phase purity, elemental distribution, and ionic conductivity. It was found that combining calcination and sintering into one process yields a higher density and ionic conductivity than splitting it into two with intermediate regrinding of the material. Impedance data indicate an increase in ionic conductivity when substituting pentavalent ions for tetravalent ones due to the resulting higher concentration of mobile charge carriers in the structure, compared to Li₆La₃Zr_0.5Nb_0.5Ta_0.5Hf_0.5O₁₂.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"5 3","pages":"211–220 211–220"},"PeriodicalIF":3.3,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsorginorgau.5c00021","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144202548","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}