Narayan Ch. Jana, Albert Escuer, Paula Brandão, Anangamohan Panja
The coordination compounds featuring a {Cu4O4} core, typically bridged by hydroxo or alkoxo groups, are particularly intriguing due to their notable magnetic property and catalytic activity. In this study, we explored the synthesis and characterization of four new Schiff base ligands and their subsequent complexation with CuII salts, which resulted in the formation of three tetranuclear complexes: [Cu4(L1)4]·2H2O (1), Cu4(L2)2(HL2)2(NO3)·5H2O (2), and [Cu4(L3)4] (3), as well as one dinuclear complex: [Cu2(L4)2] (4). These tetranuclear complexes all feature a {Cu4O4} core, but with differing coordination environments around the CuII centers. For instance, complex 1 exhibits μ3-phenoxido bridges and a distorted octahedral geometry, while complex 3 features μ3-alkoxido bridges and a square pyramidal geometry. Complex 2 displays an open cubane core with mixed μ2-phenoxido and μ3-alkoxido bridges, with both square planar (CuNO4) and octahedral (CuNO5) geometries. In addition, dinuclear complex 4 was synthesized, featuring square planar CuII centers linked by μ2-alkoxido bridges. The magnetic studies revealed that 1 and 2 exhibit strong antiferromagnetic coupling, which is attributed to their larger Cu–O–Cu bond angles, while complex 3 demonstrates moderate ferromagnetic behavior, associated with smaller bond angles. Literature reports indicate that {Cu4O4} cubane cores generally show ferromagnetic interactions at bond angles near 104°, but in complex 3, we observed moderate ferromagnetic interactions with a Cu–O–Cu bridging angle of 108.41(9)°, making it one of the highest bond angles observed for ferromagnetic interactions in a {Cu4O4} cubane-like system. The planar dinuclear complex 4 exhibits extremely strong antiferromagnetic coupling, which is attributed to the ideal Cu–O–Cu bridging angles and the planar Cu–O–O–Cu core. Additionally, EPR measurements of complex 3 at 4 K reveal a well-isolated S = 2 ground state, separated by a gap of 65.8 cm⁻¹ from the three closest degenerate spin levels (S = 0, 1, and 1). Finally, all four complexes were used as catalysts for the aerobic oxidation of 2-aminophenol, and the mechanism of the oxidation process was elucidated by EPR spectroscopy.
{"title":"Exploring structural, magnetic, and catalytic diversity in tetranuclear {Cu4O4} cubane cores and a dinuclear complex derived from closely related ligand systems","authors":"Narayan Ch. Jana, Albert Escuer, Paula Brandão, Anangamohan Panja","doi":"10.1039/d4dt03283g","DOIUrl":"https://doi.org/10.1039/d4dt03283g","url":null,"abstract":"The coordination compounds featuring a {Cu4O4} core, typically bridged by hydroxo or alkoxo groups, are particularly intriguing due to their notable magnetic property and catalytic activity. In this study, we explored the synthesis and characterization of four new Schiff base ligands and their subsequent complexation with CuII salts, which resulted in the formation of three tetranuclear complexes: [Cu4(L1)4]·2H2O (1), Cu4(L2)2(HL2)2(NO3)·5H2O (2), and [Cu4(L3)4] (3), as well as one dinuclear complex: [Cu2(L4)2] (4). These tetranuclear complexes all feature a {Cu4O4} core, but with differing coordination environments around the CuII centers. For instance, complex 1 exhibits μ3-phenoxido bridges and a distorted octahedral geometry, while complex 3 features μ3-alkoxido bridges and a square pyramidal geometry. Complex 2 displays an open cubane core with mixed μ2-phenoxido and μ3-alkoxido bridges, with both square planar (CuNO4) and octahedral (CuNO5) geometries. In addition, dinuclear complex 4 was synthesized, featuring square planar CuII centers linked by μ2-alkoxido bridges. The magnetic studies revealed that 1 and 2 exhibit strong antiferromagnetic coupling, which is attributed to their larger Cu–O–Cu bond angles, while complex 3 demonstrates moderate ferromagnetic behavior, associated with smaller bond angles. Literature reports indicate that {Cu4O4} cubane cores generally show ferromagnetic interactions at bond angles near 104°, but in complex 3, we observed moderate ferromagnetic interactions with a Cu–O–Cu bridging angle of 108.41(9)°, making it one of the highest bond angles observed for ferromagnetic interactions in a {Cu4O4} cubane-like system. The planar dinuclear complex 4 exhibits extremely strong antiferromagnetic coupling, which is attributed to the ideal Cu–O–Cu bridging angles and the planar Cu–O–O–Cu core. Additionally, EPR measurements of complex 3 at 4 K reveal a well-isolated S = 2 ground state, separated by a gap of 65.8 cm⁻¹ from the three closest degenerate spin levels (S = 0, 1, and 1). Finally, all four complexes were used as catalysts for the aerobic oxidation of 2-aminophenol, and the mechanism of the oxidation process was elucidated by EPR spectroscopy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"5 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929442","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}
Proton pump inhibitors (PPIs), metabolized by cytochrome P450 (P450) enzymes, are widely used to inhibit gastric acid secretion. This study investigated CYP116B46, a self-sufficient monooxygenase with a reductase domain, to elucidate its interaction with ilaprazole, a PPI. Binding assays and docking simulations indicate that CYP116B46 serves as a suitable model for studying PPI metabolism.
{"title":"Biophysical interactions between self-sufficient cytochrome P450 from Tepidiphilus thermophilus and ilaprazole","authors":"Jaejeong You, Yunha Hwang, Yeonju Jeong, Soo-Jin Yeom, Chul-Ho Yun, Hyun Goo Kang, Seung Jae Lee","doi":"10.1039/d4dt03320e","DOIUrl":"https://doi.org/10.1039/d4dt03320e","url":null,"abstract":"Proton pump inhibitors (PPIs), metabolized by cytochrome P450 (P450) enzymes, are widely used to inhibit gastric acid secretion. This study investigated CYP116B46, a self-sufficient monooxygenase with a reductase domain, to elucidate its interaction with ilaprazole, a PPI. Binding assays and docking simulations indicate that CYP116B46 serves as a suitable model for studying PPI metabolism.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"4 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929436","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}
Tao Wang, Bin Li, ZhangYu Zhang, Shuting Xu, Jun Wang, Jianwei Zheng, Hao Li, Feng-Jun Zhang, Xiaolong Fang
A universal and green catalytic system for the hydrogenation of unsaturated aldehydes and ketones into the corresponding alcohols with the retained C=C bonds under atmospheric hydrogen pressure in water phase was realized by N-functionalized amino ligands stablized ruthenium complexes (o-PPh2C6H4NHMe)[(CH2NHR)2]RuCl2 (R = H, Me, Et) and (o-PPh2C6H4NMe2)[(CH2NHEt)2]RuCl2 with wide substrate compatibility and excellent functionality tolerance. The structural synergism between o-PPh2C6H4NHMe and (CH2NHEt)2 achieves the enhanced performances, with a positive correlation to the electron density of the amino ligand.
{"title":"Ambient-Pressure Selective Hydrogenation of Unsaturated Aldehydes and Ketones into Unsaturated Alcohols in Water Phase","authors":"Tao Wang, Bin Li, ZhangYu Zhang, Shuting Xu, Jun Wang, Jianwei Zheng, Hao Li, Feng-Jun Zhang, Xiaolong Fang","doi":"10.1039/d4dt03338h","DOIUrl":"https://doi.org/10.1039/d4dt03338h","url":null,"abstract":"A universal and green catalytic system for the hydrogenation of unsaturated aldehydes and ketones into the corresponding alcohols with the retained C=C bonds under atmospheric hydrogen pressure in water phase was realized by N-functionalized amino ligands stablized ruthenium complexes (o-PPh2C6H4NHMe)[(CH2NHR)2]RuCl2 (R = H, Me, Et) and (o-PPh2C6H4NMe2)[(CH2NHEt)2]RuCl2 with wide substrate compatibility and excellent functionality tolerance. The structural synergism between o-PPh2C6H4NHMe and (CH2NHEt)2 achieves the enhanced performances, with a positive correlation to the electron density of the amino ligand.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"5 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929438","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}
Jie Gou, Can Yang, YunJie Wang, Yaolong Zhu, Qingwen Zhu, Xin Su, Qi Wu
The quest for novel nonlinear optical (NLO) polymorphs is pivotal for advancing laser technology and frequency conversion applications. We present a detailed study on the synthesis and properties of the Fdd2 polymorph of C12H8N2O4Zn, which exhibits an enhanced second harmonic generation (SHG) effect, 0.3 times that of KDP, nearly 8-fold higher than the P43212 phase. This improvement is attributed to an increased [ZnN2O4] polyhedral stacking angle and structural distortion in the Fdd2 phase. Our findings underscore the importance of polymorphs in optimizing NLO properties and position the Fdd2 phase as a promising candidate for ultraviolet NLO applications.
{"title":"Enhanced Second Harmonic Generation in a Fdd2 polymorph of C12H8N2O4Zn for UV Nonlinear Optical Applications","authors":"Jie Gou, Can Yang, YunJie Wang, Yaolong Zhu, Qingwen Zhu, Xin Su, Qi Wu","doi":"10.1039/d4dt03179b","DOIUrl":"https://doi.org/10.1039/d4dt03179b","url":null,"abstract":"The quest for novel nonlinear optical (NLO) polymorphs is pivotal for advancing laser technology and frequency conversion applications. We present a detailed study on the synthesis and properties of the Fdd2 polymorph of C12H8N2O4Zn, which exhibits an enhanced second harmonic generation (SHG) effect, 0.3 times that of KDP, nearly 8-fold higher than the P43212 phase. This improvement is attributed to an increased [ZnN2O4] polyhedral stacking angle and structural distortion in the Fdd2 phase. Our findings underscore the importance of polymorphs in optimizing NLO properties and position the Fdd2 phase as a promising candidate for ultraviolet NLO applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"19 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929756","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}
MITA HALDER, Diana Castillo Cardenas, Angela M M. Chartouni, Damien Culver
(PhPNHP)Ru(H)(Cl)(CO) serves as a precatalyst to a variety of important catalytic transformations but most improvements have been restricted to the pincer or replacement of the CO ligand cis to the hydride or changing the Ph groups of the pincer for other aryl or alkyl groups. The ligand trans to the hydride is often another hydride and studies that utilize other trans ligands in catalysis are limited. In this work, we synthesized a series of [(PhPNHP)Ru(H)(CO)(L)][BPh4] complexes bearing isonitrile, PMe3, or a N-heterocyclic ligand trans to the Ru-H. We compared the new complexes abilities to catalyze the transfer hydrogenation of ketones. We found that all the trans ligands improved the chemoselectivity and stability of the catalysts; and strong π-accepting ligands resulted in poor catalytic activities whereas strong σ-donating ligands accelerated the catalysis.
{"title":"Catalysis Activity and Chemoselectivity Control with the Trans Ligand in Ru-H Pincer Complexes","authors":"MITA HALDER, Diana Castillo Cardenas, Angela M M. Chartouni, Damien Culver","doi":"10.1039/d4dt03491k","DOIUrl":"https://doi.org/10.1039/d4dt03491k","url":null,"abstract":"(PhPNHP)Ru(H)(Cl)(CO) serves as a precatalyst to a variety of important catalytic transformations but most improvements have been restricted to the pincer or replacement of the CO ligand cis to the hydride or changing the Ph groups of the pincer for other aryl or alkyl groups. The ligand trans to the hydride is often another hydride and studies that utilize other trans ligands in catalysis are limited. In this work, we synthesized a series of [(PhPNHP)Ru(H)(CO)(L)][BPh4] complexes bearing isonitrile, PMe3, or a N-heterocyclic ligand trans to the Ru-H. We compared the new complexes abilities to catalyze the transfer hydrogenation of ketones. We found that all the trans ligands improved the chemoselectivity and stability of the catalysts; and strong π-accepting ligands resulted in poor catalytic activities whereas strong σ-donating ligands accelerated the catalysis.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"29 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935396","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}
This perpective delves into the emerging field of matere bonds, a novel type of noncovalent interaction involving group 7 elements such as manganese, technetium, and rhenium. Matere bonds, a new member of the σ-hole family where metal atoms act as electron acceptors, have been shown experimentally and theoretically to play significant roles in the self-assembly and stabilization of supramolecular structures both in solid-state and solution-phase environments. This perspective article explores the physical nature of these interactions, emphasizing their directionality and structural influence in various supramolecular architectures. Recent studies have expanded the understanding of matere bonds beyond classical metal-ligand coordination, highlighting their potential in crystal engineering and catalysis. This perspective article also examines the occurrence of matere bonds in biological systems, particularly within manganese-containing proteins, where they contribute to the structural integrity and catalytic activity. Theoretical and computational analyses, including molecular electrostatic potential surfaces and density functional theory, further elucidate the properties and applications of matere bonds, offering new insights for the design of advanced materials and biomimetic systems. This comprehensive overview underscores the versatility of matere bonds, paving the way for future innovations in supramolecular chemistry involving metals
{"title":"The Matere Bond","authors":"Rosa Maria Gomila, Antonio Frontera","doi":"10.1039/d4dt03302g","DOIUrl":"https://doi.org/10.1039/d4dt03302g","url":null,"abstract":"This perpective delves into the emerging field of matere bonds, a novel type of noncovalent interaction involving group 7 elements such as manganese, technetium, and rhenium. Matere bonds, a new member of the σ-hole family where metal atoms act as electron acceptors, have been shown experimentally and theoretically to play significant roles in the self-assembly and stabilization of supramolecular structures both in solid-state and solution-phase environments. This perspective article explores the physical nature of these interactions, emphasizing their directionality and structural influence in various supramolecular architectures. Recent studies have expanded the understanding of matere bonds beyond classical metal-ligand coordination, highlighting their potential in crystal engineering and catalysis. This perspective article also examines the occurrence of matere bonds in biological systems, particularly within manganese-containing proteins, where they contribute to the structural integrity and catalytic activity. Theoretical and computational analyses, including molecular electrostatic potential surfaces and density functional theory, further elucidate the properties and applications of matere bonds, offering new insights for the design of advanced materials and biomimetic systems. This comprehensive overview underscores the versatility of matere bonds, paving the way for future innovations in supramolecular chemistry involving metals","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"80 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929440","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}
Three-component crown ether phase change materials are characterized by a structural phase change in response to external stimuli such as temperature, and electric or magnetic fields, resulting in significant changes in physical properties. In this work, we designed and synthesized two novel host-guest crown ether molecules [(PTFMA)(15-crown-5)ClO4] (1) and [(PTFMA)(15-crown-5)PF6] (2), by reaction of p-trifluoromethylaniline (PTFMA) with 15-crown-5 in perchloric acid or hexafluorophosphoric acid aqueous solution. Compound 1 changes from the noncentrosymmetric space group (P21) to the centrosymmetric space group (P21/c) with increasing temperature, and exhibits a switchable SHG signal and an obvious dielectric response and corresponds to a reversible DSC phase transition. In contrast to compound 1, compound 2 is in the center space group and does not exhibit switchable SHG signals. The difference in properties between the two compounds may be due to the polarity modulation of the anion, providing new ideas for obtaining crown ether complexes with SHG response properties.
{"title":"Anionic Modulation Induces Molecular Polarity in a Three-Component Crown Ether System","authors":"Feiyan Liu, Guoyong Chen, Xiao Liu, Ting Jiang, Wenjing Guo, Xiancai Li, Zhenhong Wei","doi":"10.1039/d4dt03466j","DOIUrl":"https://doi.org/10.1039/d4dt03466j","url":null,"abstract":"Three-component crown ether phase change materials are characterized by a structural phase change in response to external stimuli such as temperature, and electric or magnetic fields, resulting in significant changes in physical properties. In this work, we designed and synthesized two novel host-guest crown ether molecules [(PTFMA)(15-crown-5)ClO4] (1) and [(PTFMA)(15-crown-5)PF6] (2), by reaction of p-trifluoromethylaniline (PTFMA) with 15-crown-5 in perchloric acid or hexafluorophosphoric acid aqueous solution. Compound 1 changes from the noncentrosymmetric space group (P21) to the centrosymmetric space group (P21/c) with increasing temperature, and exhibits a switchable SHG signal and an obvious dielectric response and corresponds to a reversible DSC phase transition. In contrast to compound 1, compound 2 is in the center space group and does not exhibit switchable SHG signals. The difference in properties between the two compounds may be due to the polarity modulation of the anion, providing new ideas for obtaining crown ether complexes with SHG response properties.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929443","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}
Arno Estival, Luis Enrique Blancarte, Loïc Pinto, Romane Pointis, Nathan Galas, Alix Saquet, Laure Vendier, Rosa Santillan, Norberto Farfán, Jean-Baptiste Sortais, Mary Grellier, Antoine Simonneau
Functional pincer ligands that engage in metal-ligand cooperativity and/or are capable of redox non-innocence have found a great deal of success in catalysis. Those two properties may be found for metal complexes of the 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands. With this goal in mind, we have attempted the coordination of 2,6-bis(5-trifluoromethylpyrazol-3-yl)pyridine (LCF₃) and its tBu analogue 2,6-bis(5-tert-butylpyrazol-3-yl)pyridine (LtBu) to Mo(0) by reactions with mixed phosphine/carbonyle complexes [Mo(CO)2(MeCN)n–1(PMe3–nPhn)5–n] 1–3 (1 ≤ n ≤3). These afforded mixtures of several Mo compounds among which low yields of heptacoordinated Mo(II) complexes [Mo(CO)2(bpp)(PMe3–nPhn)2] 4a–c (LCF₃-supported) and 5a–c (LtBu-supported) bearing a doubly deprotonated bpp ligand were systematically produced. More selective syntheses of 4a–c and 5a–c were achieved by repeating these experiments in the presence of an oxidant (AgOAc or Ag–O), with moderate to good yields. 4a–c and 5a–c were characterized by the means of NMR, IR and UV-Vis spectroscopies, sc-XRD as well as cyclic and square-wave voltammetry for 4a,b and 5b. The deprotonated LtBu ligand in 5a–c is re-protonated with 2 equiv. HOTf to afford the dicationic [Mo(CO)2(LtBu)(PMe3–nPhn)2][OTf]2 complexes 6a-c. Acidic treatment of 4a–c led to the decomposition of the complexes.
{"title":"Synthesis and Characterization of Heptacoordinated Molybdenum(II) Complexes Supported with 2,6-Bis(pyrazol-3-yl)pyridine (bpp) Ligands","authors":"Arno Estival, Luis Enrique Blancarte, Loïc Pinto, Romane Pointis, Nathan Galas, Alix Saquet, Laure Vendier, Rosa Santillan, Norberto Farfán, Jean-Baptiste Sortais, Mary Grellier, Antoine Simonneau","doi":"10.1039/d4dt03264k","DOIUrl":"https://doi.org/10.1039/d4dt03264k","url":null,"abstract":"Functional pincer ligands that engage in metal-ligand cooperativity and/or are capable of redox non-innocence have found a great deal of success in catalysis. Those two properties may be found for metal complexes of the 2,6-bis(pyrazol-3-yl)pyridine (bpp) ligands. With this goal in mind, we have attempted the coordination of 2,6-bis(5-trifluoromethylpyrazol-3-yl)pyridine (LCF₃) and its <small><sup><em>t</em></sup></small>Bu analogue 2,6-bis(5-tert-butylpyrazol-3-yl)pyridine (L<small><sup><em>t</em>Bu</sup></small>) to Mo(0) by reactions with mixed phosphine/carbonyle complexes [Mo(CO)<small><sub>2</sub></small>(MeCN)<small><sub><em>n</em>–1</sub></small>(PMe<small><sub>3–<em>n</em></sub></small>Ph<small><sub><em>n</em></sub></small>)<small><sub>5–<em>n</em></sub></small>] <strong>1</strong>–<strong>3</strong> (1 ≤ <em>n</em> ≤3). These afforded mixtures of several Mo compounds among which low yields of heptacoordinated Mo(II) complexes [Mo(CO)<small><sub>2</sub></small>(bpp)(PMe<small><sub>3–<em>n</em></sub></small>Ph<small><sub><em>n</em></sub></small>)<small><sub>2</sub></small>] <strong>4a</strong>–<strong>c</strong> (L<small><sup>CF₃</sup></small>-supported) and <strong>5a</strong>–<strong>c</strong> (L<small><sup><em>t</em>Bu</sup></small>-supported) bearing a doubly deprotonated bpp ligand were systematically produced. More selective syntheses of <strong>4a</strong>–<strong>c</strong> and <strong>5a</strong>–<strong>c</strong> were achieved by repeating these experiments in the presence of an oxidant (AgOAc or Ag<small><sub>–</sub></small>O), with moderate to good yields. <strong>4a</strong>–<strong>c</strong> and <strong>5a</strong>–<strong>c</strong> were characterized by the means of NMR, IR and UV-Vis spectroscopies, sc-XRD as well as cyclic and square-wave voltammetry for <strong>4a</strong>,<strong>b</strong> and <strong>5b</strong>. The deprotonated L<small><sup><em>t</em>Bu</sup></small> ligand in <strong>5a</strong>–<strong>c</strong> is re-protonated with 2 equiv. HOTf to afford the dicationic [Mo(CO)<small><sub>2</sub></small>(L<small><sup><em>t</em>Bu</sup></small>)(PMe<small><sub>3–<em>n</em></sub></small>Ph<small><sub>n</sub></small>)<small><sub>2</sub></small>][OTf]<small><sub>2</sub></small> complexes <strong>6a</strong>-<strong>c</strong>. Acidic treatment of <strong>4a</strong>–<strong>c</strong> led to the decomposition of the complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929755","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 reactions of the sterically demanding ferrocenyl lithium dimer (Fc*Li)2 (Fc* = 2,5-bis(3,5-di-t-butyl-phenyl)-1-ferrocenyl) with aluminum trihalides (AlCl3, AlBr3, and AlI3) to furnish the corresponding bis(ferrocenyl)haloalumanes are reported. In the case of the reaction with AlI3, an unexpected intramolecular 1,1’-aluminum migration in the ferrocenyl moiety was found to occur. Their monomeric structures with a tri-coordinated aluminum atom show affinitive Al···Fe interactions
{"title":"Monomeric Tri-coordinated Bis(ferrocenyl)haloalumanes","authors":"Togo Anzai, Koh Sugamata, Takahiro Sasamori","doi":"10.1039/d4dt03233k","DOIUrl":"https://doi.org/10.1039/d4dt03233k","url":null,"abstract":"The reactions of the sterically demanding ferrocenyl lithium dimer (Fc*Li)2 (Fc* = 2,5-bis(3,5-di-t-butyl-phenyl)-1-ferrocenyl) with aluminum trihalides (AlCl3, AlBr3, and AlI3) to furnish the corresponding bis(ferrocenyl)haloalumanes are reported. In the case of the reaction with AlI3, an unexpected intramolecular 1,1’-aluminum migration in the ferrocenyl moiety was found to occur. Their monomeric structures with a tri-coordinated aluminum atom show affinitive Al···Fe interactions","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"97 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142924893","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}
In the history of magnetochemistry development, lanthanide-transition (3d-4f) heterometallic compounds have been considered an attractive candidate for magnetic refrigerant. Herein, a series of heterometallic compounds have been designed templated by C2O42- anions, that is, {[Ln2Ni(L)(C2O4)2(H2O)2]·H2O}n [Ln = GdIII (abbr. Gd2Ni), = SmIII (abbr. Sm2Ni), = TbIII (abbr. Tb2Ni), H2C2O4 = oxalic acid; H4L = ethylene diamine tetraacetic acid]. The structural analysis reveals that Ln2Ni compounds feature a C2O42--templated wavy-shaped two-dimensional layer. Then, adjacent wavy-shaped layers are further aggregated by C2O42– anions, resulting in an innovative three-dimensional metal-organic framework. Magnetization analysis revealed that Gd2Ni exhibits a favorable −ΔSmmax of 38.0 J kg-1 K-1 at 2.0 K for 7.0 T. Besides, the C2O42--templates anchored in the architecture display a decent magnetocaloric effect at low-field (−ΔSm = 25.1 J kg−1 K −1 at 2.0 T for 2.0 K and −ΔSm =14.5 J kg−1 K −1 at 1.0 T for 2.0 K), outperforming most 3d-4f heterometallic compounds reported previously.
{"title":"C2O42--Templated [Ln2Ni] Heterometallic Compounds for Enhanced Magnetocaloric Effect at Low-Field","authors":"Qin Wang, Lingxi Xu, Jilei Wang, Yating Yu, Xu Bai, Chutian Jiang, Qiao-Ling Chen, Yan Xu","doi":"10.1039/d4dt03056g","DOIUrl":"https://doi.org/10.1039/d4dt03056g","url":null,"abstract":"In the history of magnetochemistry development, lanthanide-transition (3d-4f) heterometallic compounds have been considered an attractive candidate for magnetic refrigerant. Herein, a series of heterometallic compounds have been designed templated by C2O42- anions, that is, {[Ln2Ni(L)(C2O4)2(H2O)2]·H2O}n [Ln = GdIII (abbr. Gd2Ni), = SmIII (abbr. Sm2Ni), = TbIII (abbr. Tb2Ni), H2C2O4 = oxalic acid; H4L = ethylene diamine tetraacetic acid]. The structural analysis reveals that Ln2Ni compounds feature a C2O42--templated wavy-shaped two-dimensional layer. Then, adjacent wavy-shaped layers are further aggregated by C2O42– anions, resulting in an innovative three-dimensional metal-organic framework. Magnetization analysis revealed that Gd2Ni exhibits a favorable −ΔSmmax of 38.0 J kg-1 K-1 at 2.0 K for 7.0 T. Besides, the C2O42--templates anchored in the architecture display a decent magnetocaloric effect at low-field (−ΔSm = 25.1 J kg−1 K −1 at 2.0 T for 2.0 K and −ΔSm =14.5 J kg−1 K −1 at 1.0 T for 2.0 K), outperforming most 3d-4f heterometallic compounds reported previously.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"27 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917604","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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