European Journal of Inorganic Chemistry最新文献_第5页

The Tuning of Structure Types and Switchable Dielectric Behavior in Pyridine Bromocuprate (II) Complexes 溴铜酸吡啶（II）配合物结构类型的调整和介电行为的可切换

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-20 DOI: 10.1002/ejic.202500287

Meng-Long Liu, Xiang Hao, Yue-Qing Hu, Wan-Ying Zhang, Ping-Ping Shi

{"title":"The Tuning of Structure Types and Switchable Dielectric Behavior in Pyridine Bromocuprate (II) Complexes","authors":"Meng-Long Liu, Xiang Hao, Yue-Qing Hu, Wan-Ying Zhang, Ping-Ping Shi","doi":"10.1002/ejic.202500287","DOIUrl":"https://doi.org/10.1002/ejic.202500287","url":null,"abstract":"Stimuli-responsive phase transition materials exhibiting reversible switching between distinct dielectric states have emerged as promising candidates for applications in memory storage, logic circuits, and smart sensors. However, a fundamental challenge remaining is the lack of in-depth understanding of the structure-property relationships that govern phase transitions. Herein, a comparative study of three pyridine-based copper (II) bromide compounds is given, [C5NH6]2[CuBr4] (1), [CuBr2(C5NH5)2] (2), and [(C5NH6)2(18-crown-6)2][CuBr4] (3), falling into three different structural categories: a zero-dimensional organic–inorganic hybrid, a coordination complex, and a supramolecular host-guest compound, respectively. Among them, only compound 1 has a distinct order–disorder phase transition accompanied by switchable dielectric property. Structural analyses and Hirshfeld surface studies reveal that the loosely packed hybrid framework of compound 1 enables moderate intermolecular interactions and sufficient motional freedom of the pyridinium cations, thereby dominating the phase transition. In contrast, for compounds 2 and 3, such molecular motions are significantly suppressed by the stronger coordination bonding or hydrogen bonds. These findings emphasize the decisive role of competition between molecular motions and suitable intermolecular interactions in modulating structural phase transitions, offering valuable insights into the crystal engineering of functional materials with dielectric switching behaviors.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 26","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135465","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

An Experimental and Theoretical Investigation of the Ethylene Oligomerization Reactions Catalyzed by Heterocyclic (Pyrazolyl)Imine Fe(II) and Co(II) Complexes 杂环（吡唑基）亚胺铁（II）和钴（II）配合物催化乙烯低聚反应的实验和理论研究

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-20 DOI: 10.1002/ejic.202500248

Francis K. Migwi, George S. Nyamato, Matthew P. Akerman, Stephen O. Ojwach

{"title":"An Experimental and Theoretical Investigation of the Ethylene Oligomerization Reactions Catalyzed by Heterocyclic (Pyrazolyl)Imine Fe(II) and Co(II) Complexes","authors":"Francis K. Migwi, George S. Nyamato, Matthew P. Akerman, Stephen O. Ojwach","doi":"10.1002/ejic.202500248","DOIUrl":"10.1002/ejic.202500248","url":null,"abstract":"Reactions of heterocyclic (pyrazolyl)imine ligands (L1-L4) with CoCl2 or FeCl2 yield the complexes Co(L1)Cl2 (Co1), Fe(L1)Cl2 (Fe1), Co(L2)Cl2 (Co2), Co(L3)Cl2 (Co3), and Co(L4)Cl2 (Co4) in good yields. These complexes are structurally characterized using FT-IR spectroscopy, mass spectrometry, magnetic moment measurements, elemental analysis, and single crystal X-ray diffraction for Co1 and Co4. The molecular structures of Co1 and Co4 confirm the formation of tridentate N^N^N and bidentate N^N bound monometallic complexes, respectively. Density functional theory calculations show the Co2 is most shielded (92.72%), while Co4 is the least shielded (74.11%). On the other hand, complex Fe1 displays the lowest NBO charge of 1.163, while Co2 has the highest NBO charge of 1.358. Activation of the complexes with either EtAlCl2 or MAO cocatalysts forms active catalysts in ethylene oligomerization reactions to afford mainly ethylene dimers (C4) and trimers (C6). The catalytic performance of these complexes is influenced by the nature of the coordinated ligand and metal atom and is largely controlled by the relative stability of the active species. The tridentate complex Co1 (5.32 × 104 g (product) mol−1Co h−1) is more active than the bidentate bound analogs Co3 and Co4, while catalyst Fe1 displays the highest catalytic activity of 9.66 × 104 g (product) mol−1Fe h.−1","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 25","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500248","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145058093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enantiopure Phosphine Oxides with Electron-Rich Chiral Rhenium Stereocenters: Syntheses, Structures, and Brønsted Basicities 具有富电子手性铼立体中心的对映纯磷氧化物：合成、结构和Brønsted碱度

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-20 DOI: 10.1002/ejic.202500260

Sandra Eichenseher, Florian Friedlein, Michael J. O’Brien, Michael B. Hall, Frank Hampel, John A. Gladysz

{"title":"Enantiopure Phosphine Oxides with Electron-Rich Chiral Rhenium Stereocenters: Syntheses, Structures, and Brønsted Basicities","authors":"Sandra Eichenseher, Florian Friedlein, Michael J. O’Brien, Michael B. Hall, Frank Hampel, John A. Gladysz","doi":"10.1002/ejic.202500260","DOIUrl":"https://doi.org/10.1002/ejic.202500260","url":null,"abstract":"The chiral racemic methyl complex (η5-C5R5)Re(NO)(PPh3)(CH3) (2) is converted to the rhenium-containing phosphorus donor ligands (η5-C5R5)Re(NO)(PPh3)((CH2)nPR'2) (n/R/R’ = a, 0/H/Ph; 4b, 0/H/t-Bu; 7a, 0/Me/Ph; 10a, 1/H/Ph; 10b, 1/H/t-Bu) via standard sequences involving intermediate phosphonium salts (4a,b and 7a; TfOH/CH2Cl2 or HBF4/chlorobenzene, then PR2H, then t-BuOK; 10a,b, Ph3C+ X−, then PR2H, then t-BuOK). These are converted to the title phosphine oxides (η5-C5R5)Re(NO)(PPh3)((CH2)nP(O)R'2) (n/R/R’ = 1a, 0/H/Ph; 1b, 0/H/t-Bu; 8a, 0/Me/Ph; 11a, 1/H/Ph; 11b, 1/H/t-Bu) using PhIO, Me3SiOOSiMe3 or (for 8a) air. The enantiopure methyl complex (S)-2 is similarly converted to (R)-4a,b, (R)-8a, and (S)-11a,b. The crystal structures of 1a, (S)-1a·(H2O)0.5, (S)-8a, and 11a·CHCl3 are determined. The basicities of PO-containing species play key roles in certain enantioselective catalytic reactions. Those of the title and related compounds are computed by DFT (i.a. 8b > 8a > 1b > 1a > 11b > 11a > t-Bu3PO > Ph3PO). The enhancements in the rhenium-containing species are rationalized.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 27","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500260","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196918","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Osmium(VI) Nitrido Complexes with Perfluorinated Alcoholate Ligands: Expanding Ligand Scope through a Simple Silver Oxide-Mediated Synthesis Route 锇（VI）氮配合物与全氟醇配体：通过简单的氧化银介导的合成路线扩大配体范围

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-20 DOI: 10.1002/ejic.202500335

Joshua Parche, Robin Sievers, Tim-Niclas Streit, Moritz Malischewski

{"title":"Osmium(VI) Nitrido Complexes with Perfluorinated Alcoholate Ligands: Expanding Ligand Scope through a Simple Silver Oxide-Mediated Synthesis Route","authors":"Joshua Parche, Robin Sievers, Tim-Niclas Streit, Moritz Malischewski","doi":"10.1002/ejic.202500335","DOIUrl":"https://doi.org/10.1002/ejic.202500335","url":null,"abstract":"The coordination of perfluorinated alcohols toward an osmium(VI) nitrido center is described. Herein, [NBu4][OsNCl4] is reacted with hexafluoroacetone hydrate (HFA), perfluoropinacol (PFP), or pentafluorophenol (C6F5OH) in the presence of Ag2O to obtain the stable complexes [NBu4][Os(N)(O2C(CF3)2)2] (1), [NBu4][Os(N)(O2C2(CF3)4)2] (2), [NBu4][Os(N)(OC6F5)4] (3), and [NBu4][Os(N)(Cl)2(O2C(CF3)2)] (4) in overall good yields. These complexes represent rare examples of Os(VI) nitrido complexes that carry four O-donor ligands, as no examples have been reported for perfluorinated alcoholates so far. Complexes 1 and 4 extend the coordination chemistry of the otherwise underrepresented O2C(CF3)2 ligand. The latter offers the potential for further functionalization of the osmium(VI) nitrido complex through substitution of the remaining chloride ligands. The compounds are fully characterized, and the crystal structures of compounds 1, 2, and 3 are analyzed.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 26","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500335","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Zinc and Cobalt Coordination Polymers Based on the Redox-Active Linker 4,4′-(Phenazine-5,10-diyl)dibenzoate: Structures and Electrochemical Properties 基于氧化还原活性连接剂4,4′-（吩那嗪-5,10-二酰基）二苯甲酸酯的锌钴配位聚合物：结构和电化学性能

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-19 DOI: 10.1002/ejic.202500270

Dietrich Püschel, Moritz Nau, Nabil Assahub, Thi Hai Yen Beglau, Nils Hufnagel, Dustin Jordan, Tobias Heinen, Till Strothmann, Markus Suta, Rainer F. Winter, Christoph Janiak

{"title":"Zinc and Cobalt Coordination Polymers Based on the Redox-Active Linker 4,4′-(Phenazine-5,10-diyl)dibenzoate: Structures and Electrochemical Properties","authors":"Dietrich Püschel, Moritz Nau, Nabil Assahub, Thi Hai Yen Beglau, Nils Hufnagel, Dustin Jordan, Tobias Heinen, Till Strothmann, Markus Suta, Rainer F. Winter, Christoph Janiak","doi":"10.1002/ejic.202500270","DOIUrl":"10.1002/ejic.202500270","url":null,"abstract":"The novel coordination polymers [Zn(PZDB)(DEF)2]n (Zn-PZDB) and [Co(HPZDB)2(DEF)2]n (Co-HPZDB) (H2PZDB = 4,4′-(phenazine-5,10-diyl)dibenzoic acid, DEF = N,N-diethylformamide) are synthesized solvothermally from the metal nitrate salts and the linear H2PZDB linker with the redox-active phenazine-5,10-diyl core. Zn–PZDB is composed of zigzag chains with the Zn ion tetrahedrally coordinated by two diethylformamide (DEF) molecules and two carboxyl O-atoms from the bridging PZDB2− linker. The crystal structure of Co-PZDB represents a two-dimensional (2D) coordination grid. The Co2+ ion is octahedrally coordinated by two DEF molecules and four carboxyl oxygen atoms of the semi-deprotonated HPZDB− linker molecules. Yellow Zn-PZDB and red Co-PZDB turn green upon air exposure, which is due to linker oxidation, forming the (H)PZDB+ radical cation. UV/Vis/NIR spectroelectrochemistry reveals that Me2PZDB undergoes two reversible one-electron oxidations, producing characteristic absorption bands. Similar spectroscopic changes are observed upon oxidation of Zn-PZDB and Co-HPZDB. Chemical oxidation with SbCl5 yields the same color changes together with electron paramagnetic resonance signals typical of ligand-based radical cations. These findings indicate that the PZDB linker is the primary redox site. Ligand oxidation is followed by disintegration of the coordination polymers.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 25","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500270","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

The Elusive Chemistry of Pyrroloquinoline Quinone Dimethyl Ester Lanthanide Complexes in Biomimetic Alcohol Oxidation 吡咯喹啉醌二甲酯镧系配合物在仿生醇氧化中的难以捉摸的化学反应

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-15 DOI: 10.1002/ejic.202500102

Ioana Ciubotaru, Lisa C. Biener, Violeta A. Vetsova, Patrick Weis, Michael Seitz, Lena J. Daumann

{"title":"The Elusive Chemistry of Pyrroloquinoline Quinone Dimethyl Ester Lanthanide Complexes in Biomimetic Alcohol Oxidation","authors":"Ioana Ciubotaru, Lisa C. Biener, Violeta A. Vetsova, Patrick Weis, Michael Seitz, Lena J. Daumann","doi":"10.1002/ejic.202500102","DOIUrl":"10.1002/ejic.202500102","url":null,"abstract":"Since its discovery, pyrroloquinoline quinone (PQQ) has been under constant investigation regarding its efficiency in biomimetic complexes for alcohol dehydrogenation. The discovery of lanthanide (Ln) dependent methanol dehydrogenases has led to the use of lanthanide complexes bearing PQQ derivatives to oxidize alcohols. However, the mechanism of these oxidations is still a subject of debate. Herein, La3+ and Lu3+ complexes of PQQ dimethyl ester (PQQDME), that are able to stoichiometrically oxidize an alcohol substrate, are reported. In the presence of air, some catalytic turnover is observed, but less than with other, more heavily modified PQQ biomimetics known in the literature. To investigate the reason for this low turnover, the reduced counterpart, PQQDMEH2, is synthesized. It is shown that in the presence of atmospheric oxygen, the complexes of the reduced form undergo oxidation and can then also convert alcohol to aldehyde. Additionally, the involvement of radicals in the alcohol oxidation reaction and the origin and nature of these radicals is investigated.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500102","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144915092","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis and Coordination of Isomeric Phosphinoferrocene Sulfonates 同分异构体磷酸二铁磺酸盐的合成与配位

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-15 DOI: 10.1002/ejic.202500321

Martin Zábranský, Petr Štěpnička

{"title":"Synthesis and Coordination of Isomeric Phosphinoferrocene Sulfonates","authors":"Martin Zábranský, Petr Štěpnička","doi":"10.1002/ejic.202500321","DOIUrl":"https://doi.org/10.1002/ejic.202500321","url":null,"abstract":"Two isomeric phosphinoferrocene sulfonic acids representing methylene congeners of 1′-(diphenylphosphino)ferrocene-1-sulfonic acid, viz. Ph2PCH2fcSO3H (HL1) and Ph2PfcCH2SO3H (HL2, fc = ferrocene-1,1′-diyl) are synthesized and isolated as the stable crystalline ammonium salts (Et3NH)L1 and (Et2NH2)L2. Additional salts with 1,4-diazabicyclo[2.2.2]octane (dabco), namely, (dabcoH2)(L1)2 and (dabcoH)L2, are prepared for structural characterization by single-crystal X-ray diffraction analysis. Salts (Et3NH)L1 and (Et2NH2)L2 are further studied as ligands in palladium(II) complexes containing the [2-(dimethylamino-κN)methyl]phenyl-κC1 (LNC) auxiliary ligand. With [(LNC)Pd(μ-Cl)]2, the salts reacted under cleavage of the dimeric precursor to produce anionic phosphine complexes (Et3NH)[(LNC)PdCl(L1-κP)] and (Et2NH2)[(LNC)PdCl(L2-κP)]. Subsequent chloride removal with AgNO3 or, alternatively, the direct reaction of (Et3NH)L1 and (Et2NH2)L2 with the acetate-bridged dimer [(LNC)Pd(μ-OAc)]2 afforded the corresponding neutral phosphinosulfonate complexes that crystallized as the cyclic O,P-bridged trimer [(LNC)PdCl(μ(P,O)-L1)]3 and hexamer [(LNC)PdCl(μ(P,O)-L2)]6, respectively. This behavior highlights the hybrid and hemilabile nature of the heteroditopic phosphinosulfonate donors in reactions with the soft Pd(II) ions.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 30","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500321","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145341727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bioinspired Cobalt Amino Acid Complexes for Synthesis of Polyester Polyols from Epoxide and Cyclic Anhydride 环氧化物和环酸酐合成聚酯多元醇的仿生钴氨基酸配合物

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-15 DOI: 10.1002/ejic.202500197

Andrés Castro-Ruiz, Hilmir G. Guðjónsson, Berglind Runarsdottir, Sigridur G. Suman

{"title":"Bioinspired Cobalt Amino Acid Complexes for Synthesis of Polyester Polyols from Epoxide and Cyclic Anhydride","authors":"Andrés Castro-Ruiz, Hilmir G. Guðjónsson, Berglind Runarsdottir, Sigridur G. Suman","doi":"10.1002/ejic.202500197","DOIUrl":"https://doi.org/10.1002/ejic.202500197","url":null,"abstract":"The design of bioinspired catalysts offers a promising route to sustainable polyester synthesis. Herein, a series of chiral cobalt(III) amino acid complexes are introduced as highly efficient catalysts for epoxide/cyclic anhydride ring-opening copolymerization (ROCOP). Structure–activity studies reveal that complex 2, featuring a polar organosoluble side chain, exhibits exceptional catalytic performance, achieving turnover frequency (TOF) = 1151 h−1 in CHO/PA ROCOP at 100 °C with DMAP-comparable to state-of-the-art Cr(III)-salen catalysts. Furthermore, complex 3, which features a lysine-derived ligand, shows improved reactivity at elevated anhydride ratios, indicating an influence from the outer coordination sphere on catalysis. Mechanistic analysis reveals a zero-order dependence on anhydride concentration, confirming that the propagation step saturates the catalyst. Further, complex 2 maintains high TOF (1164 h−1) even in the presence of a chain transfer agent, enabling precise molecular weight control. This work illustrates tuning by an amino acid ligand as a powerful strategy for developing efficient, selective, and sustainable ROCOP catalysts, bridging the gap between bioinspired design and high-performance polymerization.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 26","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Insights into the Base-Stabilized Silylene Nature of the IrSi Bond in Ir(III)–(κ2-NSi) Complexes with 2-Quinolone and 2-Pyridone Type Ligands Ir(III) - (κ2-NSi)与2-喹诺酮和2-吡酮型配体配合物中Ir - Si键的碱稳定硅烯性质的研究

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-15 DOI: 10.1002/ejic.202500294

Marina Padilla, María Batuecas, Pilar García-Orduña, Luis A. Oro, Francisco José Fernández-Alvarez

{"title":"Insights into the Base-Stabilized Silylene Nature of the IrSi Bond in Ir(III)–(κ2-NSi) Complexes with 2-Quinolone and 2-Pyridone Type Ligands","authors":"Marina Padilla, María Batuecas, Pilar García-Orduña, Luis A. Oro, Francisco José Fernández-Alvarez","doi":"10.1002/ejic.202500294","DOIUrl":"https://doi.org/10.1002/ejic.202500294","url":null,"abstract":"A series of Ir–(κ2-NSi) complexes with 2-quinolone type ligands have been prepared and characterized to increase our scope of 16e unsaturated Ir–(κ2-NSi) species to carry out a comprehensive study of the nature of the IrSi bond. Density functional theory calculations with natural bond orbital and quantum theory of atoms in molecules analyses of a range of Ir–silyl(ene) complexes allows the description of the IrSi bond of the examinated complexes as a polarized covalent interaction. The findings of this study also suggest that the most accurate description of this bond in the Ir–(κ2-NSi) complexes is base-stabilized silylene. Investigating the silicon environment has been the key for determining the nature of the IrSi bond. This insight also enables to elucidate the base-stabilized TM–silylene character in other complexes.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 27","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500294","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145196772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Valence Conversion to Improve the Ultrabroadband Shortwave Infrared Emission Performance of Cr3+-Doped Olivine-Type Phosphor 价态转换提高Cr3+掺杂橄榄石型荧光粉的超宽带短波红外发射性能

IF 2 4区化学

European Journal of Inorganic Chemistry Pub Date : 2025-08-14 DOI: 10.1002/ejic.202500231

Lifang Yuan, Haoyi Wu, Yahong Jin

{"title":"Valence Conversion to Improve the Ultrabroadband Shortwave Infrared Emission Performance of Cr3+-Doped Olivine-Type Phosphor","authors":"Lifang Yuan, Haoyi Wu, Yahong Jin","doi":"10.1002/ejic.202500231","DOIUrl":"https://doi.org/10.1002/ejic.202500231","url":null,"abstract":"Broadband near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) have garnered considerable attention across various fields. Nevertheless, the development of long-wavelength NIR phosphors with high efficiency is still hindered. Herein, chromium-doped olivine-type phosphor LiScSiO4 via a high-temperature solid-state reaction method is successfully synthesized. Under excitation by 470 nm, the as-obtained phosphor exhibits an ultrabroadband shortwave infrared (SWIR) emission centered at 1190 nm with a full-width at half maximum (FWHM) of 325 nm. The SWIR emission intensity is enhanced by controlling the hydrogen atmosphere, which suppresses the formation of Cr4+ and promotes the transformation of Cr4+ into Cr3+. The internal quantum efficiency (IQE) and absorption efficiency (AE) of LiScSiO4:Cr3+ reach 73.46% and 46.5%, respectively. The Huang–Rhys factor of 11.4 indicates a strong electron-phonon coupling (EPC) effect, contributing to the large FWHM. Finally, encapsulating the as-obtained SWIR phosphors into a prototype pc–LED yields an SWIR output power of 20.07 mW at a driving current of 950 mA, rendering applications for night vision and online detection of water content in alcohol.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 28","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145272825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0