Iogann Tolbatov, Tiziano Marzo, Paolo Umari, Diego La Mendola, Alessandro Marrone
Paddlewheel complexes of bimetallic scaffolds are emerging metallic agents in the bioinorganic chemistry landscape. In the most commonly employed construct, these complexes are decorated by carboxylate moiety, prompting their possible deployment to target either protein or nucleic acid targets. In this study, density functional investigation was performed to assess viable mechanistic routes for the substitution of one acetate ligand with one chelating purine, i.e. adenine or guanine, in diruthenium and dirhodium tetraacetate paddlewheel complexes. This study evidenced the relevant stages of the process at an atomistic scale of resolution and provided for the encompassed rate-determining chemical events. Therefore, calculations indicated that the acetate decomplexation, as well as the concomitant nucleobase bridging proceeded gradually via a multistep process that included the leaving acetate protonation. The present picture of the mechanism is envisioned to be relevant to the design and interpretation of experiments focused on the reaction of diruthenium and/or dirhodium tetracarboxylate complexes with nucleobases and eventuating in the formation of either nucleobase bridged-complexes or in the dismantling of the bimetallic construct.
{"title":"Detailed mechanism of DNA/RNA nucleobase substituting bridging ligand in diruthenium (II,III) and dirhodium (II,II) tetraacetato paddlewheel complexes: Protonation of the leaving acetate is crucial","authors":"Iogann Tolbatov, Tiziano Marzo, Paolo Umari, Diego La Mendola, Alessandro Marrone","doi":"10.1039/d4dt02621g","DOIUrl":"https://doi.org/10.1039/d4dt02621g","url":null,"abstract":"Paddlewheel complexes of bimetallic scaffolds are emerging metallic agents in the bioinorganic chemistry landscape. In the most commonly employed construct, these complexes are decorated by carboxylate moiety, prompting their possible deployment to target either protein or nucleic acid targets. In this study, density functional investigation was performed to assess viable mechanistic routes for the substitution of one acetate ligand with one chelating purine, i.e. adenine or guanine, in diruthenium and dirhodium tetraacetate paddlewheel complexes. This study evidenced the relevant stages of the process at an atomistic scale of resolution and provided for the encompassed rate-determining chemical events. Therefore, calculations indicated that the acetate decomplexation, as well as the concomitant nucleobase bridging proceeded gradually via a multistep process that included the leaving acetate protonation. The present picture of the mechanism is envisioned to be relevant to the design and interpretation of experiments focused on the reaction of diruthenium and/or dirhodium tetracarboxylate complexes with nucleobases and eventuating in the formation of either nucleobase bridged-complexes or in the dismantling of the bimetallic construct.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"63 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Z. Chai, Tingting Gu, Annaelle Beau, Frederic Bolze, Claude P Gros, Liang Xu, Donghai Shi, Hai-Jun Xu
Four BODIPY dyes (6a ~ 6d) with electron-donating or electron-withdrawing groups at the meso-position were synthesized by Sonogashira coupling reaction of thieno[3,2-b]thiophene with mono-iodo-BODIPY moiety. All compounds were fully characterized by 1H NMR and MALDI-TOF MS. Their photophysical and electrochemical properties were studied by UV-visible absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy, two-photon excitation spectroscopy and cyclic voltammetry. These conjugated dyes exhibit interesting photophysical properties such as high molar extinction coefficient, large Stokes shift and high two-photon absorption cross section σ2.
{"title":"Thieno[3,2-b]thiophene based-bridged BODIPY dimer: synthesis, e-chem, one- and two-photon photophysical properties","authors":"Z. Chai, Tingting Gu, Annaelle Beau, Frederic Bolze, Claude P Gros, Liang Xu, Donghai Shi, Hai-Jun Xu","doi":"10.1039/d4dt02655a","DOIUrl":"https://doi.org/10.1039/d4dt02655a","url":null,"abstract":"Four BODIPY dyes (6a ~ 6d) with electron-donating or electron-withdrawing groups at the meso-position were synthesized by Sonogashira coupling reaction of thieno[3,2-b]thiophene with mono-iodo-BODIPY moiety. All compounds were fully characterized by 1H NMR and MALDI-TOF MS. Their photophysical and electrochemical properties were studied by UV-visible absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy, two-photon excitation spectroscopy and cyclic voltammetry. These conjugated dyes exhibit interesting photophysical properties such as high molar extinction coefficient, large Stokes shift and high two-photon absorption cross section σ2.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"29 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xiang Kun Cui, Yu Ding, Li Feng, Li Ming Chen, Yang Mei Hu, Hui Chen, Chong-Qing Wan
Herein, we report a new type solid-state electrolyte based on MOF matrix and Li+ ionic liquid. By covalent bonding the Li+ ionic liquids (MIMS·LiTFSI) on the stable UiO-67 framework, the obtained crystallineILLi-MOF material exhibited high ion conductivities within the wide temperature range (30 oC 1.62 × 10-3 S cm-1, 110 oC 1.26 × 10-2 S cm-1) and efficient Li+ transport (tLi+ = 0.88) [MIMS: 1-(1-mthyl-3-imidazolio) propane-3-sulfonate), LiTFSI: lithium bis(trifluoromethane sulfonyl)imide]. Characterization and control experiment showed the ordered structure of ionic-liquid moiety (MIMS·LiTFSI) arranged along the infinite channel with the ultramicropore (< 1 nm) in the MOF well accounted for the high and efficient target Li+ transfer. Also，such two in one strategy endows such crystalline electrolyte with the merits such as umflammalbe property, stable and unleakage desired.
{"title":"Ionic-liquid Functionalized Metal-organic Framework and Its High Performance Solid Electrolyte for Lithium-ion Conduction","authors":"Xiang Kun Cui, Yu Ding, Li Feng, Li Ming Chen, Yang Mei Hu, Hui Chen, Chong-Qing Wan","doi":"10.1039/d4dt02756f","DOIUrl":"https://doi.org/10.1039/d4dt02756f","url":null,"abstract":"Herein, we report a new type solid-state electrolyte based on MOF matrix and Li+ ionic liquid. By covalent bonding the Li+ ionic liquids (MIMS·LiTFSI) on the stable UiO-67 framework, the obtained crystallineILLi-MOF material exhibited high ion conductivities within the wide temperature range (30 oC 1.62 × 10-3 S cm-1, 110 oC 1.26 × 10-2 S cm-1) and efficient Li+ transport (tLi+ = 0.88) [MIMS: 1-(1-mthyl-3-imidazolio) propane-3-sulfonate), LiTFSI: lithium bis(trifluoromethane sulfonyl)imide]. Characterization and control experiment showed the ordered structure of ionic-liquid moiety (MIMS·LiTFSI) arranged along the infinite channel with the ultramicropore (< 1 nm) in the MOF well accounted for the high and efficient target Li+ transfer. Also，such two in one strategy endows such crystalline electrolyte with the merits such as umflammalbe property, stable and unleakage desired.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Thi Hong Quan Vu, Bartosz Bondzior, Dagmara Stefanska, Shovan Dan, Przemysław Jacek Dereń
The increasing demand for highly sensitive optical thermometers operating within a wide temperature range necessitates the development of new phosphors. In this work, the potential of temperature sensing performance of a novel yellow-emitting phosphor, Sr2MgWO6 double perovskite, doped with varying concentrations of Dy3+ was investigated for the first time. Increasing the concentration of Dy3+ from 0% to 7% shifted the color of luminescence from blue to yellowish-orange within the CIE1931 color space. The energy transfer efficiency from (WO6)6- to Dy3+ also increased significantly to 98.4%. Moreover, the sample doped with 3% Dy3+ showed the highest emission intensity, with concentration beyond this threshold inducing concentration quenching. This phenomenon was primarily governed by dipole-dipole interactions. The highest quantum yield was found to be 30.7% for the sample doped with 3%Dy3+. Upon 266 nm excitation wavelength, the temperature sensing ability of the samples doped with 3%, 5%, and 7%Dy3+ was examined based on the fluorescent intensity ratio between thermally coupled and uncoupled levels. It showed that the relative thermal sensitivity of Sr can be tuned by changing the Dy3+ concentration. Sr-max = 3.24%K-1 was obtained for the sample doped with 3%Dy3+ at 193 K within the 80 - 273 K operating range for thermally uncoupled levels. For thermally coupled levels, the Sr-max value reached 1.35%K-1 at 333 K for the sample doped with 7%Dy3+ in the range of 293 – 593 K. These results demonstrated the enormous potential of the studied materials for thermal sensing application.
{"title":"A highly sensitive ratiometric optical thermometer based on Sr2MgWO6 double perovskite doped with Dy3+ exploiting thermally coupled and uncoupled levels","authors":"Thi Hong Quan Vu, Bartosz Bondzior, Dagmara Stefanska, Shovan Dan, Przemysław Jacek Dereń","doi":"10.1039/d4dt02940b","DOIUrl":"https://doi.org/10.1039/d4dt02940b","url":null,"abstract":"The increasing demand for highly sensitive optical thermometers operating within a wide temperature range necessitates the development of new phosphors. In this work, the potential of temperature sensing performance of a novel yellow-emitting phosphor, Sr2MgWO6 double perovskite, doped with varying concentrations of Dy3+ was investigated for the first time. Increasing the concentration of Dy3+ from 0% to 7% shifted the color of luminescence from blue to yellowish-orange within the CIE1931 color space. The energy transfer efficiency from (WO6)6- to Dy3+ also increased significantly to 98.4%. Moreover, the sample doped with 3% Dy3+ showed the highest emission intensity, with concentration beyond this threshold inducing concentration quenching. This phenomenon was primarily governed by dipole-dipole interactions. The highest quantum yield was found to be 30.7% for the sample doped with 3%Dy3+. Upon 266 nm excitation wavelength, the temperature sensing ability of the samples doped with 3%, 5%, and 7%Dy3+ was examined based on the fluorescent intensity ratio between thermally coupled and uncoupled levels. It showed that the relative thermal sensitivity of Sr can be tuned by changing the Dy3+ concentration. Sr-max = 3.24%K-1 was obtained for the sample doped with 3%Dy3+ at 193 K within the 80 - 273 K operating range for thermally uncoupled levels. For thermally coupled levels, the Sr-max value reached 1.35%K-1 at 333 K for the sample doped with 7%Dy3+ in the range of 293 – 593 K. These results demonstrated the enormous potential of the studied materials for thermal sensing application.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The ethynylation of formaldehyde reaction catalyzed by Cu-based catalysts is an important synthesis method for 1,4-butynediol relating to high value-added chemicals. In this work, a series of CuM/SiO2 ( M=Bi, Mg, Mn ) catalysts were prepared by a deposition-precipitation method and applied in the ethynylation reaction. The effects of different promoters ( Bi, Mg, Mn ) on the catalytic activity were investigated. The relationship between catalyst structure and performance is systematically studied using XRD, TEM, SEM mapping, N2 low- temperature adsorption/desorption, FT-IR, XPS, and TG-DTA characterization analysis. The results show that 30Cu2Bi/SiO2 exhibits the highest 1,4-butynediol yield (70%) and selectivity (97%) after the ethynylation reaction for 7 h. Furthermore, compared with the commercial catalyst, 30Cu2Bi/SiO2 shows similar cyclic stability, 47% yield, and 98% selectivity for 1,4-butynediol after 8 times about 60 h. It is attributed that small CuO particles are uniformly dispersed in 30Cu2Bi/SiO2 with the biggest specific surface area (446.37 m2/g). What’s more, the Cu-Bi interface existing in 30Cu2Bi/SiO2 plays an important role in stabilizing cuprous, not excessively reduced to metallic Cu. Therefore, during the ethynylation reaction, 30Cu2Bi/SiO2 has the most active Cu2C2 and the least polyacetylene by-products. In addition, the richest oxygen vacancies arose in 30Cu2Bi/SiO2 also contribute to the ethynylation of the formaldehyde reaction.
{"title":"The preparation of CuM/SiO2 (M=Bi, Mg, Mn) catalysts applied in ethynylation of formaldehyde for 1,4‑butynediol synthesis: the positive interface effect of CuO and Bi2O3","authors":"Jiali Chen, Guihua Yang, Feng Gao, Rui Wang","doi":"10.1039/d4dt02616k","DOIUrl":"https://doi.org/10.1039/d4dt02616k","url":null,"abstract":"The ethynylation of formaldehyde reaction catalyzed by Cu-based catalysts is an important synthesis method for 1,4-butynediol relating to high value-added chemicals. In this work, a series of CuM/SiO2 ( M=Bi, Mg, Mn ) catalysts were prepared by a deposition-precipitation method and applied in the ethynylation reaction. The effects of different promoters ( Bi, Mg, Mn ) on the catalytic activity were investigated. The relationship between catalyst structure and performance is systematically studied using XRD, TEM, SEM mapping, N2 low- temperature adsorption/desorption, FT-IR, XPS, and TG-DTA characterization analysis. The results show that 30Cu2Bi/SiO2 exhibits the highest 1,4-butynediol yield (70%) and selectivity (97%) after the ethynylation reaction for 7 h. Furthermore, compared with the commercial catalyst, 30Cu2Bi/SiO2 shows similar cyclic stability, 47% yield, and 98% selectivity for 1,4-butynediol after 8 times about 60 h. It is attributed that small CuO particles are uniformly dispersed in 30Cu2Bi/SiO2 with the biggest specific surface area (446.37 m2/g). What’s more, the Cu-Bi interface existing in 30Cu2Bi/SiO2 plays an important role in stabilizing cuprous, not excessively reduced to metallic Cu. Therefore, during the ethynylation reaction, 30Cu2Bi/SiO2 has the most active Cu2C2 and the least polyacetylene by-products. In addition, the richest oxygen vacancies arose in 30Cu2Bi/SiO2 also contribute to the ethynylation of the formaldehyde reaction.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600031","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rebekah N. Duffin, Jenisi Kelderman, Megan Herdman, Philip Craig Andrews
Five complexes of gallium derived from hydroxamic acids have been synthesised, characterised, and their anti-bacterial activity and mammalian cell toxicity established. These are three metal-organic complexes; [Ga(BPHA]3 1, [Ga(BHA-H]3 2, [Ga(SHA-H2)(SHA-H)]3 3, and two heteroleptic organometallic complexes [GaMe2(BPHA)] 4, and [GaMe(BHA-H)2] 5, along with the iron complex [Fe(BPHA)3] 6 (BPHA-H = N-benzoyl-N-phenylhydroxamic acid, BHA-H2 = phenylhydroxamic acid, and SHA-H3 = salicylhydroxamic acid). Solid-state structures of 1, 4 – 6 were identified by single-crystal X-ray crystallography. Complexes 1 and 6 adopt an octahedral geometry at the metal centre, while the organometallic complexes 4 and 5 adopt, respectively, tetrahedral and trigonal bipyramidal geometry. The solution and solid-state chemistry of complex 3 was found to differ: the solution state is composed of an equilibrium mixture of the bis-complexed hydroximate-hydroxamate species and the homoleptic tris-hydroxamate species, with the solid state preferring the bis-complexed hydroximate-hydroxamate composition. The methyl gallium complexes 4 and 5 differed in their preferred composition with 4 forming the expected dimethyl hydroxamate complex while 5 stabilises as the methyl bis-hydroxamate complex. Complexes were tested for the anti-microbial activity against a series of Gram-positive and Gram-negative bacteria, with an emphasis on the Gram-negative Klebsiella pneumoniae. While the metal-organic complexes 1, 2, 3 and 6 showed little to no activity towards either the bacteria or mammalian cells, the alkyl gallium complexes 4 and 5 were found to have exceptional activity toward K. pneumoniae in RPMI-HS media with MIC values of 78 nM. Interestingly, [GaMe2(OH)] also showed significant activity with an MIC of 156 nM.
{"title":"Highly selective organo-gallium hydroxamate mediated inhibition of antibiotic resistant Klebsiella pneumoniae","authors":"Rebekah N. Duffin, Jenisi Kelderman, Megan Herdman, Philip Craig Andrews","doi":"10.1039/d4dt02440k","DOIUrl":"https://doi.org/10.1039/d4dt02440k","url":null,"abstract":"Five complexes of gallium derived from hydroxamic acids have been synthesised, characterised, and their anti-bacterial activity and mammalian cell toxicity established. These are three metal-organic complexes; [Ga(BPHA]<small><sub>3</sub></small> 1, [Ga(BHA-H]<small><sub>3</sub></small> 2, [Ga(SHA-H<small><sub>2</sub></small>)(SHA-H)]<small><sub>3</sub></small> 3, and two heteroleptic organometallic complexes [GaMe<small><sub>2</sub></small>(BPHA)] 4, and [GaMe(BHA-H)<small><sub>2</sub></small>] 5, along with the iron complex [Fe(BPHA)<small><sub>3</sub></small>] 6 (BPHA-H = N-benzoyl-N-phenylhydroxamic acid, BHA-H2 = phenylhydroxamic acid, and SHA-H3 = salicylhydroxamic acid). Solid-state structures of 1, 4 – 6 were identified by single-crystal X-ray crystallography. Complexes 1 and 6 adopt an octahedral geometry at the metal centre, while the organometallic complexes 4 and 5 adopt, respectively, tetrahedral and trigonal bipyramidal geometry. The solution and solid-state chemistry of complex 3 was found to differ: the solution state is composed of an equilibrium mixture of the bis-complexed hydroximate-hydroxamate species and the homoleptic tris-hydroxamate species, with the solid state preferring the bis-complexed hydroximate-hydroxamate composition. The methyl gallium complexes 4 and 5 differed in their preferred composition with 4 forming the expected dimethyl hydroxamate complex while 5 stabilises as the methyl bis-hydroxamate complex. Complexes were tested for the anti-microbial activity against a series of Gram-positive and Gram-negative bacteria, with an emphasis on the Gram-negative Klebsiella pneumoniae. While the metal-organic complexes 1, 2, 3 and 6 showed little to no activity towards either the bacteria or mammalian cells, the alkyl gallium complexes 4 and 5 were found to have exceptional activity toward K. pneumoniae in RPMI-HS media with MIC values of 78 nM. Interestingly, [GaMe<small><sub>2</sub></small>(OH)] also showed significant activity with an MIC of 156 nM.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rodrigo P. Monteiro, Isabel B. Calhau, Ana C. Gomes, André D. Lopes, José P. Da Silva, Isabel S. Gonçalves, Martyn Pillinger
The CO releasing ability of the complex [CpMo(CO)3Me] (1) (Cp = η5-C5H5) has been assessed using a deoxymyoglobin-carbonmonoxymyoglobin assay. In the dark, CO release was shown to be promoted by the reducing agent sodium dithionite in a concentration-dependent manner. At lower dithionite concentrations, where dithionite-induced CO release was minimised, irradiation at 365 nm with a low-power UV lamp resulted in a strongly enhanced release of CO (half-life (t1/2) = 6.3 min), thus establishing complex 1 as a photochemically activated CO-releasing molecule. To modify the CO release behaviour of the tricarbonyl complex, the possibility of obtaining inclusion complexes between 1 and β-cyclodextrin (βCD) or cucurbit[7]uril (CB7) by liquid–liquid interfacial precipitation (1@βCD(IP)), liquid antisolvent precipitation (1@CB7), and mechanochemical ball-milling (1@βCD(BM)) was evaluated. All these methods led to the isolation of a true inclusion compound (albeit mixed with nonincluded 1 for 1@βCD(BM)), as evidenced by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and 13C{1H} magic angle spinning (MAS) NMR. PXRD showed that 1@βCD(IP) was microcrystalline with a channel-type crystal packing structure. High resolution mass spectrometry studies revealed the formation of aqueous phase 1 : 1 complexes between 1 and CB7. For 1@βCD(IP) and 1@CB7, the protective effects of the hosts led to a decrease in the CO release rates with respect to nonincluded 1. βCD had the strongest effect, with a ca. 10-fold increase in t1/4 for dithionite-induced CO release, and a ca. 2-fold increase in t1/2 for photoinduced CO release.
{"title":"β-Cyclodextrin and cucurbit[7]uril as protective encapsulation agents of the CO-releasing molecule [CpMo(CO)3Me]","authors":"Rodrigo P. Monteiro, Isabel B. Calhau, Ana C. Gomes, André D. Lopes, José P. Da Silva, Isabel S. Gonçalves, Martyn Pillinger","doi":"10.1039/d4dt01863j","DOIUrl":"https://doi.org/10.1039/d4dt01863j","url":null,"abstract":"The CO releasing ability of the complex [CpMo(CO)<small><sub>3</sub></small>Me] (<strong>1</strong>) (Cp = η<small><sup>5</sup></small>-C<small><sub>5</sub></small>H<small><sub>5</sub></small>) has been assessed using a deoxymyoglobin-carbonmonoxymyoglobin assay. In the dark, CO release was shown to be promoted by the reducing agent sodium dithionite in a concentration-dependent manner. At lower dithionite concentrations, where dithionite-induced CO release was minimised, irradiation at 365 nm with a low-power UV lamp resulted in a strongly enhanced release of CO (half-life (<em>t</em><small><sub>1/2</sub></small>) = 6.3 min), thus establishing complex <strong>1</strong> as a photochemically activated CO-releasing molecule. To modify the CO release behaviour of the tricarbonyl complex, the possibility of obtaining inclusion complexes between <strong>1</strong> and β-cyclodextrin (βCD) or cucurbit[7]uril (CB7) by liquid–liquid interfacial precipitation (<strong>1</strong>@βCD(IP)), liquid antisolvent precipitation (<strong>1</strong>@CB7), and mechanochemical ball-milling (<strong>1</strong>@βCD(BM)) was evaluated. All these methods led to the isolation of a true inclusion compound (albeit mixed with nonincluded <strong>1</strong> for <strong>1</strong>@βCD(BM)), as evidenced by powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), FT-IR and FT-Raman spectroscopies, and <small><sup>13</sup></small>C{<small><sup>1</sup></small>H} magic angle spinning (MAS) NMR. PXRD showed that <strong>1</strong>@βCD(IP) was microcrystalline with a channel-type crystal packing structure. High resolution mass spectrometry studies revealed the formation of aqueous phase 1 : 1 complexes between <strong>1</strong> and CB7. For <strong>1</strong>@βCD(IP) and <strong>1</strong>@CB7, the protective effects of the hosts led to a decrease in the CO release rates with respect to nonincluded <strong>1</strong>. βCD had the strongest effect, with a <em>ca.</em> 10-fold increase in <em>t</em><small><sub>1/4</sub></small> for dithionite-induced CO release, and a <em>ca.</em> 2-fold increase in <em>t</em><small><sub>1/2</sub></small> for photoinduced CO release.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"80 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600028","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Meysam Kakavand, Anna Kozakiewicz, Abdollah Neshat
To develop stable and efficient silver(I) catalysts and evaluate the role of sulfur and phosphorus donor ligands in the catalytic cycloaddition of selected organic azides and alkynes (AAC), a series of mononuclear Ag(I) and heteronuclear Ag(I)-Fe(II) complexes were synthesized. The synthesis utilized phosphine and sulfur donors from the dialkyldithiophosphate and borate families, specifically Na[S2H2B(mt)2]. These complexes are designated as [(dppf)AgSP(S)(OiPr)2] (1), [S2H2B(mt)2Ag(-dppf)Ag(S2H2B(mt)2] (2), [(dppf)Ag(-dppf)Ag(dppf)] (3), and [(dppe)AgS2H2B(mt)2] (5). The complexes 1-5 were characterized using a combination of 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, as well as IR spectroscopy techniques. In two instances, single-crystal X-ray diffraction analysis was also employed. Complex 3 exhibited high catalytic activity and regioselectivity in the cycloaddition reaction conducted in water at 40 °C.
为了开发稳定高效的银（I）催化剂并评估硫和磷供体配体在催化某些有机叠氮化物和炔烃 (AAC) 环化反应中的作用，我们合成了一系列单核银（I）和杂核银（I）-铁（II）配合物。合成过程利用了二烷基二硫代磷酸和硼酸盐家族中的膦和硫供体，特别是 Na[S2H2B(mt)2]。这些配合物被命名为[(dppf)AgSP(S)(OiPr)2]（1）、[S2H2B(mt)2Ag(-dppf)Ag(S2H2B(mt)2]（2）、[(dppf)Ag(-dppf)Ag(dppf)]（3）和[(dppe)AgS2H2B(mt)2]（5）。我们使用 1H、13C{1H} 和 31P{1H} 组合核磁共振光谱对 1-5 复合物进行了表征。核磁共振光谱以及红外光谱技术对复合物 1-5 进行了表征。有两次还采用了单晶 X 射线衍射分析。配合物 3 在 40 °C 的水中进行环加成反应时表现出很高的催化活性和区域选择性。
{"title":"Stable homogeneous silver(I) catalysts for the highly efficient cycloaddition of azides onto terminal alkynes in water","authors":"Meysam Kakavand, Anna Kozakiewicz, Abdollah Neshat","doi":"10.1039/d4dt02825b","DOIUrl":"https://doi.org/10.1039/d4dt02825b","url":null,"abstract":"To develop stable and efficient silver(I) catalysts and evaluate the role of sulfur and phosphorus donor ligands in the catalytic cycloaddition of selected organic azides and alkynes (AAC), a series of mononuclear Ag(I) and heteronuclear Ag(I)-Fe(II) complexes were synthesized. The synthesis utilized phosphine and sulfur donors from the dialkyldithiophosphate and borate families, specifically Na[S2H2B(mt)2]. These complexes are designated as [(dppf)AgSP(S)(OiPr)2] (1), [S2H2B(mt)2Ag(-dppf)Ag(S2H2B(mt)2] (2), [(dppf)Ag(-dppf)Ag(dppf)] (3), and [(dppe)AgS2H2B(mt)2] (5). The complexes 1-5 were characterized using a combination of 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, as well as IR spectroscopy techniques. In two instances, single-crystal X-ray diffraction analysis was also employed. Complex 3 exhibited high catalytic activity and regioselectivity in the cycloaddition reaction conducted in water at 40 °C.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"95 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600029","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sai Kumar Gobbilla, Kulsum Bano, Priyabrata Biswal, Soumyadip Dey, Ravi Kumar, Abhijit Sau, Vadapalli Chandrasekhar, Tarun Kanti Panda
Herein, we report the synthesis of three indium complexes (1-3) supported by different chelating ligands (L1-L3). The indium metal complexes were characterized by using multinuclear NMR, and their solid-state structures were confirmed by single-crystal X-ray crystallography. The indium complex 1 (5 mol%) effectively reduced nitroarenes in the presence of phenylsilane and NaI. Nitroarenes containing different functionalities were reduced under standard conditions to give the corresponding amines in good yields.
在此，我们报告了由不同螯合配体（L1-L3）支持的三种铟配合物（1-3）的合成过程。我们利用多核核磁共振对这些铟金属配合物进行了表征，并通过单晶 X 射线晶体学证实了它们的固态结构。铟配合物 1（5 摩尔%）在苯基硅烷和 NaI 的存在下有效地还原了硝基烯烃。在标准条件下，含有不同官能度的硝基arenes 被还原，并以良好的产率得到相应的胺。
{"title":"Indium-Catalyzed Hydrosilylation of Nitroarenes to Aromatic Amines","authors":"Sai Kumar Gobbilla, Kulsum Bano, Priyabrata Biswal, Soumyadip Dey, Ravi Kumar, Abhijit Sau, Vadapalli Chandrasekhar, Tarun Kanti Panda","doi":"10.1039/d4dt02861a","DOIUrl":"https://doi.org/10.1039/d4dt02861a","url":null,"abstract":"Herein, we report the synthesis of three indium complexes (1-3) supported by different chelating ligands (L1-L3). The indium metal complexes were characterized by using multinuclear NMR, and their solid-state structures were confirmed by single-crystal X-ray crystallography. The indium complex 1 (5 mol%) effectively reduced nitroarenes in the presence of phenylsilane and NaI. Nitroarenes containing different functionalities were reduced under standard conditions to give the corresponding amines in good yields.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"5 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zinc–air batteries are recognized for their environmental friendliness and high energy density; however, the slow kinetics of the oxygen reduction reaction (ORR) at the air electrode hinder their commercial viability. The research focuses on synthesizing cubic hollow carbon structures derived from Metal–Organic Frameworks (MOFs), which enhance catalytic performance through improved conductivity and mass transfer. The resulting Fe/Fe3C/HCNB catalyst demonstrates a half-wave potential of 0.826 V for ORR and achieves a peak power density of 274 mW cm−2 in zinc–air batteries, surpassing commercial Pt/C catalysts. Electrochemical impedance spectroscopy reveals that the hollow structure enhances hydrophilicity and reduces solution resistance, facilitating greater active site engagement in electrochemical reactions. The study concludes that the unique structural features of Fe/Fe3C/HCNB significantly improve discharge performance and stability, positioning it as a promising alternative for zinc–air battery applications.
{"title":"Fe/Fe3C particles encapsulated in hollow carbon nanoboxes for high performance zinc–air batteries","authors":"Chuyun Huang, Wenyuan Zhang, Xuezhi Hu, Shiliang Fei, Fhulufhelo Nemangwele, Nnditshedzeni Eric Maluta, Yangsen Hu, Hui Lv, Pei Hu, Zhuo Peng","doi":"10.1039/d4dt02396j","DOIUrl":"https://doi.org/10.1039/d4dt02396j","url":null,"abstract":"Zinc–air batteries are recognized for their environmental friendliness and high energy density; however, the slow kinetics of the oxygen reduction reaction (ORR) at the air electrode hinder their commercial viability. The research focuses on synthesizing cubic hollow carbon structures derived from Metal–Organic Frameworks (MOFs), which enhance catalytic performance through improved conductivity and mass transfer. The resulting Fe/Fe<small><sub>3</sub></small>C/HCNB catalyst demonstrates a half-wave potential of 0.826 V for ORR and achieves a peak power density of 274 mW cm<small><sup>−2</sup></small> in zinc–air batteries, surpassing commercial Pt/C catalysts. Electrochemical impedance spectroscopy reveals that the hollow structure enhances hydrophilicity and reduces solution resistance, facilitating greater active site engagement in electrochemical reactions. The study concludes that the unique structural features of Fe/Fe<small><sub>3</sub></small>C/HCNB significantly improve discharge performance and stability, positioning it as a promising alternative for zinc–air battery applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"37 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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