The three-dimensional (3D) cyano-based organic–inorganic hybrid double perovskites (CHOIPs) have shown great application potential in the field of multifunctional materials due to their unique ferroelasticity, ferroelectricity, and dielectric-switching properties. However, the inherent spatial limitations of the 3D rigid framework greatly restrict the types and sizes of organic cations that can be introduced, and they limit the further regulation and optimization of material properties. A zero-dimensional (0D) CHOIPs ferroelastic material, (MA)3[Fe(CN)6] (MA = CH3NH3+), was reported to break through this limitation, providing an idea for the development of 0D CHOIPs phase-transition materials, but reports on 0D CHOIPs ferroelastic phase-transition materials are still scarce. In this study, we adopted the H/F substitution strategy and synthesized two 0D organic–inorganic hybrid metal cyanide materials, (EA)3[Fe(CN)6] (EA = CH3CH2NH3+, ethylamine) and (DFEA)3[Fe(CN)6] (DFEA = F2CHCH2NH3+). The results show that the phase transition of (DFEA)3[Fe(CN)6] originates from the coupling mechanism of the ordered–disordered transformation of organic cations and the coordinated rotation of inorganic [Fe(CN)6]3– octahedrons. By introducing fluorine atoms, the phase-transition temperature is significantly higher than that of EA+. This work provides ideas for the structural design and material-property optimization of 0D organic–inorganic hybrid metal cyanides.
{"title":"H/F Substitution Strategy in 0D Organic–Inorganic Hybrid Metal Cyanides Designing Ferroelastic Phase-Transition Materials","authors":"Luan-Ying Ji,Shu-Yi Liu,Jun-Si Zhou,Zhi-Lin Liao,Si-Qi Yu,Di Gao,Huang-Dong Wang,Jian-Chun Liu,Kai-Wen Jiang,Xiao-Gang Chen","doi":"10.1021/acs.inorgchem.6c00011","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00011","url":null,"abstract":"The three-dimensional (3D) cyano-based organic–inorganic hybrid double perovskites (CHOIPs) have shown great application potential in the field of multifunctional materials due to their unique ferroelasticity, ferroelectricity, and dielectric-switching properties. However, the inherent spatial limitations of the 3D rigid framework greatly restrict the types and sizes of organic cations that can be introduced, and they limit the further regulation and optimization of material properties. A zero-dimensional (0D) CHOIPs ferroelastic material, (MA)3[Fe(CN)6] (MA = CH3NH3+), was reported to break through this limitation, providing an idea for the development of 0D CHOIPs phase-transition materials, but reports on 0D CHOIPs ferroelastic phase-transition materials are still scarce. In this study, we adopted the H/F substitution strategy and synthesized two 0D organic–inorganic hybrid metal cyanide materials, (EA)3[Fe(CN)6] (EA = CH3CH2NH3+, ethylamine) and (DFEA)3[Fe(CN)6] (DFEA = F2CHCH2NH3+). The results show that the phase transition of (DFEA)3[Fe(CN)6] originates from the coupling mechanism of the ordered–disordered transformation of organic cations and the coordinated rotation of inorganic [Fe(CN)6]3– octahedrons. By introducing fluorine atoms, the phase-transition temperature is significantly higher than that of EA+. This work provides ideas for the structural design and material-property optimization of 0D organic–inorganic hybrid metal cyanides.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.inorgchem.5c05070
Brandon T. Watson,Khadijatul Kobra Meem,Vo Quang Huy Phan,Owen Dong,Alvaro Muñoz-Castro,H. V. Rasika Dias
This study highlights the use of fluorinated poly(pyrazolyl)borate ligands to stabilize copper(I) complexes with heavy pnictogen donors such as SbPh3 and BiPh3. It presents two series of valence isoelectronic molecules, enabling a direct and meaningful comparison between the lighter and heavier analogues. Specifically, [HB(3,5-(CF3)2Pz)3]− and [H2B(3,5-(CF3)2Pz)2]− have been utilized in the stabilization of a series of copper(I) complexes with EPh3 (E = As, Sb, Bi), along with full characterization including their molecular structures and a detailed analysis of group 15 trends. The isolation of a copper–bismuthine complex, [HB(3,5-(CF3)2Pz)3]Cu(BiPh3), is especially notable as an example of a direct, unsupported Cu–Bi bond. DFT calculations show that the stabilization energy of Cu–E interactions decreases from P to Bi, illustrating the difficulty in stabilizing bismuthine ligands and the role of relativistic effects in reducing the bonding and Lewis basicity characteristics of the E coordinating center. The Cu-EPh3 bond mainly relies on electrostatic interactions, but orbital interactions are also significant, with the Ph3E→Cu σ-donation being much stronger than Ph3E←Cu π-backdonation. Reactivity studies of [HB(3,5-(CF3)2Pz)3]Cu(BiPh3) and computational investigations on how fluorinated supporting ligands on Cu(I) affect the formation of the Cu–E adduct are also included.
{"title":"Unsupported Bonds between Copper(I) and Heavier Pnictogens","authors":"Brandon T. Watson,Khadijatul Kobra Meem,Vo Quang Huy Phan,Owen Dong,Alvaro Muñoz-Castro,H. V. Rasika Dias","doi":"10.1021/acs.inorgchem.5c05070","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05070","url":null,"abstract":"This study highlights the use of fluorinated poly(pyrazolyl)borate ligands to stabilize copper(I) complexes with heavy pnictogen donors such as SbPh3 and BiPh3. It presents two series of valence isoelectronic molecules, enabling a direct and meaningful comparison between the lighter and heavier analogues. Specifically, [HB(3,5-(CF3)2Pz)3]− and [H2B(3,5-(CF3)2Pz)2]− have been utilized in the stabilization of a series of copper(I) complexes with EPh3 (E = As, Sb, Bi), along with full characterization including their molecular structures and a detailed analysis of group 15 trends. The isolation of a copper–bismuthine complex, [HB(3,5-(CF3)2Pz)3]Cu(BiPh3), is especially notable as an example of a direct, unsupported Cu–Bi bond. DFT calculations show that the stabilization energy of Cu–E interactions decreases from P to Bi, illustrating the difficulty in stabilizing bismuthine ligands and the role of relativistic effects in reducing the bonding and Lewis basicity characteristics of the E coordinating center. The Cu-EPh3 bond mainly relies on electrostatic interactions, but orbital interactions are also significant, with the Ph3E→Cu σ-donation being much stronger than Ph3E←Cu π-backdonation. Reactivity studies of [HB(3,5-(CF3)2Pz)3]Cu(BiPh3) and computational investigations on how fluorinated supporting ligands on Cu(I) affect the formation of the Cu–E adduct are also included.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.inorgchem.5c05264
Sangita Das,Dipali Karmakar,Ankita Banik,Sk Imran Ali
Acentric helical Se3 and the β-polymorph of Nb2Se3 were grown using the hydrothermal method. The existence of chirality in Se3 was demonstrated in both P3121 and P3221 enantiomorphs with lattice parameters a = 4.3654(2) Å, c = 4.9603(2) Å, V = 81.863(6) Å3, and Z = 1. The structure consists of infinite helical chains running along the c axis. Conversely, β-Nb2Se3 exhibits orthorhombic symmetry (SG: Pnma) with lattice parameters a = 11.7748(2) Å, b = 3.9719(5) Å, c = 11.6323(5) Å, V = 544.02(7) Å3, and Z = 4. The crystal structure contains infinite [Nb2Se3]∞ chains parallel to the b axis. A needle-shaped morphology was observed in both materials. Nb2Se3 and Se3 attain 94% and 73% degradation of methylene blue dye in the presence of 6% H2O2, indicating H2O2-induced dark catalysis. Both Se3 and Nb2Se3 efficiently adsorb Cr(VI) ions with qmax of 150 and 241 mg/g, respectively, and Fe(III) ions with 248 and 266 mg/g capacity, respectively. BET and ζ-potential analyses confirm that electrostatic interactions predominantly govern the adsorption processes. The antioxidant activity against DPPH exhibits 94% and 83% efficacy in 5 and 30 min with only 1 mg of Nb2Se3 and Se3 respectively, and EC50 values are 0.12 and 0.85 mg, indicating their excellent potential as antioxidants.
{"title":"Noncentrosymmetric Helical Se3 and Second Polymorph β-Nb2Se3: Synthesis, Crystal Structure, and Their Impact on Photocatalytic Methylene Blue Degradation, Adsorptive Removal of Heavy Metals, and Antioxidant Activity","authors":"Sangita Das,Dipali Karmakar,Ankita Banik,Sk Imran Ali","doi":"10.1021/acs.inorgchem.5c05264","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05264","url":null,"abstract":"Acentric helical Se3 and the β-polymorph of Nb2Se3 were grown using the hydrothermal method. The existence of chirality in Se3 was demonstrated in both P3121 and P3221 enantiomorphs with lattice parameters a = 4.3654(2) Å, c = 4.9603(2) Å, V = 81.863(6) Å3, and Z = 1. The structure consists of infinite helical chains running along the c axis. Conversely, β-Nb2Se3 exhibits orthorhombic symmetry (SG: Pnma) with lattice parameters a = 11.7748(2) Å, b = 3.9719(5) Å, c = 11.6323(5) Å, V = 544.02(7) Å3, and Z = 4. The crystal structure contains infinite [Nb2Se3]∞ chains parallel to the b axis. A needle-shaped morphology was observed in both materials. Nb2Se3 and Se3 attain 94% and 73% degradation of methylene blue dye in the presence of 6% H2O2, indicating H2O2-induced dark catalysis. Both Se3 and Nb2Se3 efficiently adsorb Cr(VI) ions with qmax of 150 and 241 mg/g, respectively, and Fe(III) ions with 248 and 266 mg/g capacity, respectively. BET and ζ-potential analyses confirm that electrostatic interactions predominantly govern the adsorption processes. The antioxidant activity against DPPH exhibits 94% and 83% efficacy in 5 and 30 min with only 1 mg of Nb2Se3 and Se3 respectively, and EC50 values are 0.12 and 0.85 mg, indicating their excellent potential as antioxidants.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"176 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.inorgchem.5c05919
Vincent Fagué,Maëlle Le Gouadec,Sonia Mallet-Ladeira,Pascal Guillo,Christophe Fliedel
We report the synthesis, characterization, and catalytic evaluation of group 10 metal complexes supported by the new 3,4-bis(dicyclohexylphosphino)furan (dcypfu) ligand. The nickel(II) (1), palladium(II) (2), and platinum(II) (3) dichloride complexes were prepared in high yields and fully characterized by multinuclear NMR spectroscopy, mass spectrometry, and X-ray diffraction studies. The catalytic performances of complexes 1 and 2 were examined toward two representative C–C and C–S bond-forming reactions. These complexes showed moderate to good activity in the Suzuki–Miyaura cross-coupling of aryl bromides with aryl boronic acids under green conditions but remained less effective than the analogous dcypt-supported systems. In contrast, nickel (pre)catalysts supported by either the dcypfu or the dcypt ligand displayed similar performances (and limitations) toward the intramolecular decarbonylative synthesis of ethers. Both complexes 1 and 2 exhibited excellent reactivity in the intramolecular decarbonylative coupling of aryl thioesters. The NiII/Zn system proved competent across a broad substrate range but was sensitive to electronic effects, whereas the PdII/K3PO4 system delivered consistently high yields regardless of substrate electronics. These results identify complex 2 as a powerful and general (pre)catalyst for decarbonylative thioether synthesis and highlight the potential of newly reported dcypfu as a versatile supporting ligand for group 10 metal catalysis.
{"title":"Inter- and Intramolecular Coupling Reactions Catalyzed by Group 10 Metal Complexes of the 3,4-Bis(dicyclohexylphosphino)furan (dcypfu) Ligand","authors":"Vincent Fagué,Maëlle Le Gouadec,Sonia Mallet-Ladeira,Pascal Guillo,Christophe Fliedel","doi":"10.1021/acs.inorgchem.5c05919","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05919","url":null,"abstract":"We report the synthesis, characterization, and catalytic evaluation of group 10 metal complexes supported by the new 3,4-bis(dicyclohexylphosphino)furan (dcypfu) ligand. The nickel(II) (1), palladium(II) (2), and platinum(II) (3) dichloride complexes were prepared in high yields and fully characterized by multinuclear NMR spectroscopy, mass spectrometry, and X-ray diffraction studies. The catalytic performances of complexes 1 and 2 were examined toward two representative C–C and C–S bond-forming reactions. These complexes showed moderate to good activity in the Suzuki–Miyaura cross-coupling of aryl bromides with aryl boronic acids under green conditions but remained less effective than the analogous dcypt-supported systems. In contrast, nickel (pre)catalysts supported by either the dcypfu or the dcypt ligand displayed similar performances (and limitations) toward the intramolecular decarbonylative synthesis of ethers. Both complexes 1 and 2 exhibited excellent reactivity in the intramolecular decarbonylative coupling of aryl thioesters. The NiII/Zn system proved competent across a broad substrate range but was sensitive to electronic effects, whereas the PdII/K3PO4 system delivered consistently high yields regardless of substrate electronics. These results identify complex 2 as a powerful and general (pre)catalyst for decarbonylative thioether synthesis and highlight the potential of newly reported dcypfu as a versatile supporting ligand for group 10 metal catalysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"284 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mixed-anion compounds incorporating multiple anionic species within a single crystal lattice can exhibit novel structural and functional properties and so have recently attracted much attention. These materials offer unique coordination environments that can lead to emergent behaviors relevant to various applications. Coordination polymers (CPs) comprising metal centers bridged by molecular anionic linkers represent a subclass of mixed-anion compounds and are of interest. In particular, CPs featuring metal–sulfur (−M–S−)n frameworks are promising candidates for optoelectronic and catalytic applications due to the unique light absorption characteristics of these materials. The present study synthesized and characterized a new visible-light-responsive Pb(II)-based CP, termed STF-1 (Science Tokyo Framework 1; [Pb(mptt)2]n, mptt = 5-mercapto-3-phenyl-1,3,4-thiadiazole-2-thiolate). This CP exhibits an optical bandgap of 2.50 ± 0.2 eV and so is responsive to visible light. STF-1 also demonstrates charge carrier transport through the mptt ligand moiety, as supported by first-principles density functional theory calculations. Photocatalytic experiments under visible light irradiation established that STF-1 selectively reduces CO2 to formate with high selectivity and minimal hydrogen evolution. Additionally, STF-1 shows activity as a pre-electrocatalyst for CO2 conversion in aqueous media.
{"title":"A Lead(II)-Based Coordination Polymer Exhibiting Photocatalytic and Electrochemical CO2 Reduction Activities","authors":"Chomponoot Suppaso,Yura Jang,Saori Ogura,Ryohei Akiyoshi,Ryuichi Nakada,Megumi Okazaki,Fumitaka Ishiwari,Kazuyoshi Ogasawara,Akinori Saeki,Daisuke Tanaka,Kazuhiko Maeda","doi":"10.1021/acs.inorgchem.5c05258","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05258","url":null,"abstract":"Mixed-anion compounds incorporating multiple anionic species within a single crystal lattice can exhibit novel structural and functional properties and so have recently attracted much attention. These materials offer unique coordination environments that can lead to emergent behaviors relevant to various applications. Coordination polymers (CPs) comprising metal centers bridged by molecular anionic linkers represent a subclass of mixed-anion compounds and are of interest. In particular, CPs featuring metal–sulfur (−M–S−)n frameworks are promising candidates for optoelectronic and catalytic applications due to the unique light absorption characteristics of these materials. The present study synthesized and characterized a new visible-light-responsive Pb(II)-based CP, termed STF-1 (Science Tokyo Framework 1; [Pb(mptt)2]n, mptt = 5-mercapto-3-phenyl-1,3,4-thiadiazole-2-thiolate). This CP exhibits an optical bandgap of 2.50 ± 0.2 eV and so is responsive to visible light. STF-1 also demonstrates charge carrier transport through the mptt ligand moiety, as supported by first-principles density functional theory calculations. Photocatalytic experiments under visible light irradiation established that STF-1 selectively reduces CO2 to formate with high selectivity and minimal hydrogen evolution. Additionally, STF-1 shows activity as a pre-electrocatalyst for CO2 conversion in aqueous media.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138947","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.inorgchem.5c04880
Jing Liao,Zi-Meng Wang,Zhi-Heng Zhou,Lei Mei,Ji-Pan Yu,Li-Yong Yuan,Zhi-Rong Liu,Kong-Qiu Hu,Wei-Qun Shi
The electron-rich moieties and aromatic conjugated units are beneficial for promoting the adsorption and capture of iodine. Based on this principle, this study uses a triazine derivative poly(carboxylic acid) ligand H6TMTTA as an organic ligand and Cu2+ as a metal node to construct a novel cage-based MOF material (IHEP-52). This (4, 6)-connected soc net features a cage-like structure [Cu12L8]. The dynamic nanochannel architecture of IHEP-52 facilitates rapid guest exchange while exhibiting exceptional iodine capture under ambient conditions. Quantitative adsorption studies reveal a maximum capacity of 366.4 mg·g–1 for iodine in cyclohexane solution (298 K) and 1763.9 mg·g–1 for iodine vapor (353 K), with equilibration achieved within 6 h at 393 K. Raman spectra and X-ray photoelectron spectroscopy (XPS) analysis demonstrate that adsorbed iodine undergoes framework-mediated disproportionation to form costabilized I3– and I5– anions within the pore structures of IHEP-52.
{"title":"[Cu12L8] Coordination Cage-Based Metal–Organic Framework for Iodine Capture","authors":"Jing Liao,Zi-Meng Wang,Zhi-Heng Zhou,Lei Mei,Ji-Pan Yu,Li-Yong Yuan,Zhi-Rong Liu,Kong-Qiu Hu,Wei-Qun Shi","doi":"10.1021/acs.inorgchem.5c04880","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04880","url":null,"abstract":"The electron-rich moieties and aromatic conjugated units are beneficial for promoting the adsorption and capture of iodine. Based on this principle, this study uses a triazine derivative poly(carboxylic acid) ligand H6TMTTA as an organic ligand and Cu2+ as a metal node to construct a novel cage-based MOF material (IHEP-52). This (4, 6)-connected soc net features a cage-like structure [Cu12L8]. The dynamic nanochannel architecture of IHEP-52 facilitates rapid guest exchange while exhibiting exceptional iodine capture under ambient conditions. Quantitative adsorption studies reveal a maximum capacity of 366.4 mg·g–1 for iodine in cyclohexane solution (298 K) and 1763.9 mg·g–1 for iodine vapor (353 K), with equilibration achieved within 6 h at 393 K. Raman spectra and X-ray photoelectron spectroscopy (XPS) analysis demonstrate that adsorbed iodine undergoes framework-mediated disproportionation to form costabilized I3– and I5– anions within the pore structures of IHEP-52.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"51 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138949","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-09DOI: 10.1021/acs.inorgchem.6c00212
Krishna Samanta,Biswarup Chakraborty
Polyoxoanions can be used as well-defined molecular metal-oxo cluster ligands for the stabilization of reactive metal-oxide cores with tunable active sites and redox properties, and these unique materials can behave as potential electrocatalysts. Herein, an Anderson-type heteropolyoxoanion, (NH4)3[Co(OH)6Mo6O18], is used to synthesize a crystalline ∼5 nm γ-FeO(OH) nanocore on which several in situ-derived {CoMox} cluster anions are covalently attached through [Fe–O–Mo] linkages, making them highly aqueous dispersed ionic nanoparticles {CoMox@FeO(OH)}, carrying a negative charge on the surface, as precedented from the zeta (ζ) potential, vibrational, and X-ray photoelectron spectroscopies. The presence of redox-active FeIII and MoVI centers in this complete inorganic nanostructure allows sequential electroreduction of FeIII centers of the FeO(OH) core at 0.81 V (vs reversible hydrogen electrode (RHE)), followed by {CoMox} cluster reduction at 0 V vs RHE. Under an applied potential of −0.6 V vs RHE, a cooperative electron injection from both the reduced γ-FeO(OH) core and the POM ligand to the aqueous nitrate at pH 3 leads to the formation of 17.56 μmol h–1 cm–2 NH3 (65%) and 26.68 μmol h–1 cm–2 H2 (25%). Under similar electrochemical conditions, the analogous material [Mo7O24]6–-protected γ-FeO(OH) {MoxOy@FeO(OH)} shows almost comparable NH3 and H2 yields, while bare γ-FeO(OH) produces nearly half of it. The better electrocatalytic performance of the POM-protected γ-FeO(OH) materials is due to a higher number of active sites and the cooperative redox participation of the core and the POM ligands. The 15N labeling experiment confirms the source of nitrogen in the produced ammonia. D2O labeling with a kinetic isotope effect of 1.2, electrokinetic study, and in situ IR spectroscopy indicate nitrate adsorption as the rate-limiting step for the electrochemical nitrate reduction reaction (eNO3RR) and the hydroxylamine pathway as the possible reaction pathway of the eNO3RR. This study, therefore, opens up scope in the design of a variety of POM-anchored metal oxides, which can have potential applications in electrochemical conversions.
{"title":"Electrochemical Nitrate Reduction through Cooperative Redox Participation of the CoMox Cluster-Anchored γ-FeO(OH) Nanocore","authors":"Krishna Samanta,Biswarup Chakraborty","doi":"10.1021/acs.inorgchem.6c00212","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00212","url":null,"abstract":"Polyoxoanions can be used as well-defined molecular metal-oxo cluster ligands for the stabilization of reactive metal-oxide cores with tunable active sites and redox properties, and these unique materials can behave as potential electrocatalysts. Herein, an Anderson-type heteropolyoxoanion, (NH4)3[Co(OH)6Mo6O18], is used to synthesize a crystalline ∼5 nm γ-FeO(OH) nanocore on which several in situ-derived {CoMox} cluster anions are covalently attached through [Fe–O–Mo] linkages, making them highly aqueous dispersed ionic nanoparticles {CoMox@FeO(OH)}, carrying a negative charge on the surface, as precedented from the zeta (ζ) potential, vibrational, and X-ray photoelectron spectroscopies. The presence of redox-active FeIII and MoVI centers in this complete inorganic nanostructure allows sequential electroreduction of FeIII centers of the FeO(OH) core at 0.81 V (vs reversible hydrogen electrode (RHE)), followed by {CoMox} cluster reduction at 0 V vs RHE. Under an applied potential of −0.6 V vs RHE, a cooperative electron injection from both the reduced γ-FeO(OH) core and the POM ligand to the aqueous nitrate at pH 3 leads to the formation of 17.56 μmol h–1 cm–2 NH3 (65%) and 26.68 μmol h–1 cm–2 H2 (25%). Under similar electrochemical conditions, the analogous material [Mo7O24]6–-protected γ-FeO(OH) {MoxOy@FeO(OH)} shows almost comparable NH3 and H2 yields, while bare γ-FeO(OH) produces nearly half of it. The better electrocatalytic performance of the POM-protected γ-FeO(OH) materials is due to a higher number of active sites and the cooperative redox participation of the core and the POM ligands. The 15N labeling experiment confirms the source of nitrogen in the produced ammonia. D2O labeling with a kinetic isotope effect of 1.2, electrokinetic study, and in situ IR spectroscopy indicate nitrate adsorption as the rate-limiting step for the electrochemical nitrate reduction reaction (eNO3RR) and the hydroxylamine pathway as the possible reaction pathway of the eNO3RR. This study, therefore, opens up scope in the design of a variety of POM-anchored metal oxides, which can have potential applications in electrochemical conversions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"109 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138950","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-08DOI: 10.1021/acs.inorgchem.5c05686
Gongjian Hu,Inzamam Abbasi,Bo Wang,Xiaona Cai,Jiashuai Liu,Dongcai Shen,Renrong Liu,Qinggang Wang,Wenjie Tao
Polyolefin elastomers (POEs) are widely used in automotive, photovoltaic film, and home appliance industries. Compared to the classic copolymerization of ethylene and α-olefin (mainly 1-butene and 1-octene), branched polyethylene (PE) bearing similar elasticity as that of the POE is getting more attention recently. A number of cationic nickel catalyst systems were established, and good to excellent elasticity was achieved. In this work, we developed a series of anilinotropone nickel complexes bearing a hemilabile ethereal group and efficiently polymerized ethylene to produce branched PE. Tensile property study revealed that PE synthesized from the Ni2 (PENi2) catalyst displayed a stress-at-break value of 7.7 MPa and a strain-at-break value of 1870%. Interestingly, the strain recovery (SR) of PENi2 (79%) is higher than that of POEs 8150 (67%) and 7447 (67%). Quantitative 13C NMR studies suggest that PENi2 has mainly a methyl branch and a higher total branching density (88/1000) than POEs 8150 (46/1000) and 7447 (76/1000).
{"title":"Polyethylene with Good Elasticity Synthesized by Anilinotropone Nickel Catalysts","authors":"Gongjian Hu,Inzamam Abbasi,Bo Wang,Xiaona Cai,Jiashuai Liu,Dongcai Shen,Renrong Liu,Qinggang Wang,Wenjie Tao","doi":"10.1021/acs.inorgchem.5c05686","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05686","url":null,"abstract":"Polyolefin elastomers (POEs) are widely used in automotive, photovoltaic film, and home appliance industries. Compared to the classic copolymerization of ethylene and α-olefin (mainly 1-butene and 1-octene), branched polyethylene (PE) bearing similar elasticity as that of the POE is getting more attention recently. A number of cationic nickel catalyst systems were established, and good to excellent elasticity was achieved. In this work, we developed a series of anilinotropone nickel complexes bearing a hemilabile ethereal group and efficiently polymerized ethylene to produce branched PE. Tensile property study revealed that PE synthesized from the Ni2 (PENi2) catalyst displayed a stress-at-break value of 7.7 MPa and a strain-at-break value of 1870%. Interestingly, the strain recovery (SR) of PENi2 (79%) is higher than that of POEs 8150 (67%) and 7447 (67%). Quantitative 13C NMR studies suggest that PENi2 has mainly a methyl branch and a higher total branching density (88/1000) than POEs 8150 (46/1000) and 7447 (76/1000).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing highly efficient, environmentally friendly, inexpensive, and readily available photocatalysts for Baeyer–Villiger (B–V) oxidation reactions is of significant importance. This study involved encapsulating Keggin–type H3PMo12O40 and H4SiW12O40 within a Cu–tr2pr framework to synthesis two novel isomorphic POM@MOFs (CT–PMo and CT–SiW), which is the first time that polyoxometalates (POMs) have been added to metal–organic frameworks (MOFs) constructed with the participation of tr2pr organic ligands. The modulation of photoelectrochemical properties and photocatalytic activity was achieved by regulating POMs. Photoelectrochemical testing revealed that CT–PMo exhibits stronger light absorption, faster charge transfer rates, lower resistance and reduced probability of recombination compared to CT–SiW. The photoinduced B–V oxidation reaction demonstrates that CT–PMo has higher catalytic activity, with a yield of 97.1% and turnover numbers and turnover frequencies of 971 and 923.0 h–1, respectively. CT–PMo is the first noble metal–free catalyst for the photoinduced B–V oxidation reaction based on the Mukaiyama method, exhibiting the highest turnover frequencies value along with outstanding structural stability and recyclability, offering broad industrial application prospects.
{"title":"Non–Noble–Metal POM@MOF for Enhancing the Visible Photoinduced Baeyer–Villiger Oxidation Reactions","authors":"Minzhen Cai,Luoning Li,Yahao Sun,Miao Wang,Pengtao Ma,Yanan Liu,Jingping Wang,Jingyang Niu","doi":"10.1021/acs.inorgchem.5c05427","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05427","url":null,"abstract":"Developing highly efficient, environmentally friendly, inexpensive, and readily available photocatalysts for Baeyer–Villiger (B–V) oxidation reactions is of significant importance. This study involved encapsulating Keggin–type H3PMo12O40 and H4SiW12O40 within a Cu–tr2pr framework to synthesis two novel isomorphic POM@MOFs (CT–PMo and CT–SiW), which is the first time that polyoxometalates (POMs) have been added to metal–organic frameworks (MOFs) constructed with the participation of tr2pr organic ligands. The modulation of photoelectrochemical properties and photocatalytic activity was achieved by regulating POMs. Photoelectrochemical testing revealed that CT–PMo exhibits stronger light absorption, faster charge transfer rates, lower resistance and reduced probability of recombination compared to CT–SiW. The photoinduced B–V oxidation reaction demonstrates that CT–PMo has higher catalytic activity, with a yield of 97.1% and turnover numbers and turnover frequencies of 971 and 923.0 h–1, respectively. CT–PMo is the first noble metal–free catalyst for the photoinduced B–V oxidation reaction based on the Mukaiyama method, exhibiting the highest turnover frequencies value along with outstanding structural stability and recyclability, offering broad industrial application prospects.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"22 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138951","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-08DOI: 10.1021/acs.inorgchem.5c05460
Ran Zhang,Qiuyu Li,Qaiser Mahmood,Shifang Yuan,Geng Ren,Yizhou Wang,Shuangshuang Liu,Wen-Hua Sun
Control of chain walking coupled with chain transfer in nickel-catalyzed ethylene polymerization offers a versatile approach to tune the polyethylene microstructure. In the present work, we report the design, synthesis, and polymerization performance of heteroatomic hydroanthracene- and dibenzosuberyl-functionalized 2,3-bis(imino)butane–nickel complexes. Single-crystal X-ray analysis revealed the close proximity of axial phenyl caps to the chelate plane. This proximity generates weak interactions with the metal center, influencing chain walking, chain transfer, and monomer insertion rates. Upon activation with ethylaluminum sesquichloride (EASC), oxadibenzosuberyl-containing precatalysts exhibited higher activity (up to 5.02 × 106 g mol–1 h–1) than thiodibenzosuberyl analogues, whereas nonheteroatomic dibenzosuberyl precatalysts achieved the highest activity (up to 10.4 × 106 g mol–1 h–1). Corresponding molecular weights followed the same trend (111.4 vs 490.9 kg mol–1), while melting points were inversely affected (117.9 vs 104.5 °C). These trends correspond to the electronic richness of steric substituents (thiodibenzosuberyl > oxadibenzosuberyl > dibenzosuberyl) and their capacity for metal–phenyl interactions, where more electron-rich groups suppress chain walking and enhance chain transfer. Temperature-dependent chain walking and β-H elimination generated vinyl- and vinylene-terminated unsaturated polyethylene (vinyl: 100% at 40 °C; vinyl/vinylene = 36/64 at 90 °C), highlighting controllable branching and unsaturation. These results establish a rational framework for the design of high-performance nickel catalysts for polyethylene synthesis.
{"title":"Suppression of Chain Walking by Heteroatom in 2,3-Bis(imino)butane–Nickel Precatalysts for Ethylene Polymerization","authors":"Ran Zhang,Qiuyu Li,Qaiser Mahmood,Shifang Yuan,Geng Ren,Yizhou Wang,Shuangshuang Liu,Wen-Hua Sun","doi":"10.1021/acs.inorgchem.5c05460","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05460","url":null,"abstract":"Control of chain walking coupled with chain transfer in nickel-catalyzed ethylene polymerization offers a versatile approach to tune the polyethylene microstructure. In the present work, we report the design, synthesis, and polymerization performance of heteroatomic hydroanthracene- and dibenzosuberyl-functionalized 2,3-bis(imino)butane–nickel complexes. Single-crystal X-ray analysis revealed the close proximity of axial phenyl caps to the chelate plane. This proximity generates weak interactions with the metal center, influencing chain walking, chain transfer, and monomer insertion rates. Upon activation with ethylaluminum sesquichloride (EASC), oxadibenzosuberyl-containing precatalysts exhibited higher activity (up to 5.02 × 106 g mol–1 h–1) than thiodibenzosuberyl analogues, whereas nonheteroatomic dibenzosuberyl precatalysts achieved the highest activity (up to 10.4 × 106 g mol–1 h–1). Corresponding molecular weights followed the same trend (111.4 vs 490.9 kg mol–1), while melting points were inversely affected (117.9 vs 104.5 °C). These trends correspond to the electronic richness of steric substituents (thiodibenzosuberyl > oxadibenzosuberyl > dibenzosuberyl) and their capacity for metal–phenyl interactions, where more electron-rich groups suppress chain walking and enhance chain transfer. Temperature-dependent chain walking and β-H elimination generated vinyl- and vinylene-terminated unsaturated polyethylene (vinyl: 100% at 40 °C; vinyl/vinylene = 36/64 at 90 °C), highlighting controllable branching and unsaturation. These results establish a rational framework for the design of high-performance nickel catalysts for polyethylene synthesis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"45 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138952","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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