Yaping Cheng, Geoffrey Gontard, Marie Noelle Rager, Abderrahim Khatyr, Michael Knorr, Hani Amouri
The Front Cover illustrates the synthesis of a family of pyrenyl-(NHC)MCl coinage metal complexes, M=CuI, AgI and AuI, (NHC=N-heterocyclic carbene). These compounds are stable and were obtained in high yields. The molecular structures of all complexes were ascertained by X-ray diffraction studies. The use of the chromophoric-(NHC) ligand endows these complexes with emissive properties in the blue region at a similar wavelength to the magical natural blue light created by phytoplankton on the surface of the ocean at nightfall. More information can be found in the Research Article by H. Amouri and co-workers.
封面展示了一系列芘-(NHC)MCl 合金属复合物（M=CuI、AgI 和 AuI，NHC=N-杂环碳烯）的合成过程。这些化合物性质稳定，产量高。通过 X 射线衍射研究确定了所有复合物的分子结构。发色-（NHC）配体的使用使这些复合物具有蓝色区域的发射特性，其波长与夜幕降临时海洋表面浮游植物发出的神奇自然蓝光波长相似。更多信息，请参阅 H. Amouri 及其合作者的研究文章。
{"title":"Front Cover: A Novel Family of Luminescent Pyrenyl-(N-Heterocyclic Carbene)- Halogenated Coinage Metal Complexes: Synthesis, Crystal Structures, and Optical Properties (Eur. J. Inorg. Chem. 27/2024)","authors":"Yaping Cheng, Geoffrey Gontard, Marie Noelle Rager, Abderrahim Khatyr, Michael Knorr, Hani Amouri","doi":"10.1002/ejic.202482701","DOIUrl":"https://doi.org/10.1002/ejic.202482701","url":null,"abstract":"<p><b>The Front Cover</b> illustrates the synthesis of a family of pyrenyl-(NHC)MCl coinage metal complexes, M=Cu<sup>I</sup>, Ag<sup>I</sup> and Au<sup>I</sup>, (NHC=<i>N</i>-heterocyclic carbene). These compounds are stable and were obtained in high yields. The molecular structures of all complexes were ascertained by X-ray diffraction studies. The use of the chromophoric-(NHC) ligand endows these complexes with emissive properties in the blue region at a similar wavelength to the magical natural blue light created by phytoplankton on the surface of the ocean at nightfall. More information can be found in the Research Article by H. Amouri and co-workers.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202482701","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142328456","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}
Dr. Maxim A. Lutoshkin, Dr. Ilya V. Taydakov, Anastasia A. Patrusheva, Dr. Petr I. Matveev
Perfluorinated β-diketones form chelation complexes with rare earth and transition metals. Six heterocyclic dicarbonyl ligands demonstrate chelation activity toward ThIV at acidic pH in aqueous solution. The “true” stability constants lie in the range 6.2–6.8 logarithmic units and are much greater than for lanthanide complexes. A significant bathochromic shift between the maximum absorption wavelength of lanthanide and actinide monocomplexes of β-diketones was detected. The spectral shift increases with the atomic number of the substituted chalcogen atom in the heterocyclic ring of the corresponding ligand. More information can be found in the Research Article by M. A. Lutoshkin and co-workers.
全氟 β-二酮与稀土和过渡金属形成螯合复合物。在酸性 pH 值的水溶液中，六种杂环二羰基配体对 ThIV 具有螯合活性。其 "真实 "稳定常数在 6.2-6.8 对数单位之间，远高于镧系元素络合物。β-二酮的镧系元素和锕系元素单络合物的最大吸收波长之间存在明显的浴色偏移。光谱偏移随相应配体杂环中取代的查耳根原子的原子序数增加而增加。更多信息可参阅 M. A. Lutoshkin 及其合作者的研究文章。Lutoshkin 及其合作者的研究文章中。
{"title":"Front Cover: Complexation of ThoriumIV with Fluorinated Heterocyclic β-Diketones in Aqueous Hydrochloric Solutions (Eur. J. Inorg. Chem. 26/2024)","authors":"Dr. Maxim A. Lutoshkin, Dr. Ilya V. Taydakov, Anastasia A. Patrusheva, Dr. Petr I. Matveev","doi":"10.1002/ejic.202482601","DOIUrl":"10.1002/ejic.202482601","url":null,"abstract":"<p><b>Perfluorinated β-diketones</b> form chelation complexes with rare earth and transition metals. Six heterocyclic dicarbonyl ligands demonstrate chelation activity toward Th<sup>IV</sup> at acidic pH in aqueous solution. The “true” stability constants lie in the range 6.2–6.8 logarithmic units and are much greater than for lanthanide complexes. A significant bathochromic shift between the maximum absorption wavelength of lanthanide and actinide monocomplexes of β-diketones was detected. The spectral shift increases with the atomic number of the substituted chalcogen atom in the heterocyclic ring of the corresponding ligand. More information can be found in the Research Article by M. A. Lutoshkin and co-workers.\u0000 <figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.2,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202482601","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250303","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}
Vidumini Suchintha Samarasiri, Tiron Jahinge, Tori Forbes
Hybrid materials, such as metal organic nanotubes (MONTs) can possess nanoconfined water molecules within their pore space and the overall behavior of the water within the material may be tuned based upon interactions with the inner channel walls. We have previously developed a range of methods (electron density mapping, kinetic models, and water interaction enthalpies) to evaluate water behavior under nanoconfinement using a uranium-based metal organic nanotube (UMONT) but have not explored their applicability across a range of materials. In the current study, we test our methodologies on two additional MONT materials (LaMONT and Cu-LaMONT) to determine if the techniques can be utilized in other systems to predict behavior within complex hybrid materials. In addition, we explored how to use Hirshfeld surface maps generated by the CrystalExplorer software in the visualization and prediction of water behavior within complex hybrid materials.
金属有机纳米管（MONTs）等混合材料的孔隙空间内可拥有纳米约束水分子，材料内水的整体行为可根据与通道内壁的相互作用进行调整。我们之前开发了一系列方法（电子密度图、动力学模型和水相互作用焓）来评估铀基金属有机纳米管（UMONT）在纳米约束下的水行为，但尚未探索这些方法在各种材料中的适用性。在本研究中，我们在另外两种 MONT 材料（LaMONT 和 Cu-LaMONT）上测试了我们的方法，以确定这些技术是否可用于其他系统，从而预测复杂混合材料的行为。此外，我们还探索了如何使用 CrystalExplorer 软件生成的 Hirshfeld 表面图来可视化和预测复杂混合材料中水的行为。
{"title":"Water Networks within Metal Organic Nanotubes: Assessment of Techniques to Understand Structure and Properties","authors":"Vidumini Suchintha Samarasiri, Tiron Jahinge, Tori Forbes","doi":"10.1002/ejic.202400327","DOIUrl":"https://doi.org/10.1002/ejic.202400327","url":null,"abstract":"Hybrid materials, such as metal organic nanotubes (MONTs) can possess nanoconfined water molecules within their pore space and the overall behavior of the water within the material may be tuned based upon interactions with the inner channel walls. We have previously developed a range of methods (electron density mapping, kinetic models, and water interaction enthalpies) to evaluate water behavior under nanoconfinement using a uranium-based metal organic nanotube (UMONT) but have not explored their applicability across a range of materials. In the current study, we test our methodologies on two additional MONT materials (LaMONT and Cu-LaMONT) to determine if the techniques can be utilized in other systems to predict behavior within complex hybrid materials. In addition, we explored how to use Hirshfeld surface maps generated by the CrystalExplorer software in the visualization and prediction of water behavior within complex hybrid materials.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268677","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}
The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand-protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M-M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.
本微综述侧重于多年来记录的金属羰基团簇（MCCs）异构现象的不同类型，并概述了它们与其他配体保护分子团簇和纳米团簇的相似之处。MCC 分子中的同分异构主要分为两大类进行讨论，即表面同分异构和核心同分异构。第一节介绍了涉及无机配体（羰基和氢化物）和有机配体的一些代表性表面异构例子，以及由装饰团簇表面的 ML 片段引起的异构现象。第二部分重点讨论三大类核异构现象，即：(1) 主要在 M-M 间距上存在差异的异构体；(2) 金属核结构不同的异构体；(3) 金属核和配体外壳几乎完全相同，但金属核内不同类型金属原子位置不同的异构体。第三节简要讨论了两种相关但非常罕见的异构情况，即聚合和配位异构。最后一节概述了一般性结论。
{"title":"Isomerism in Molecular Metal Carbonyl Clusters","authors":"Cristiana Cesari, Cristina Femoni, Francesca Forti, Maria Carmela Iapalucci, Giorgia Scorzoni, Stefano Zacchini","doi":"10.1002/ejic.202400220","DOIUrl":"https://doi.org/10.1002/ejic.202400220","url":null,"abstract":"The present microreview focuses on different typologies of isomerism documented along the years for metal carbonyl clusters (MCCs), and outlines their analogies to other classes of ligand-protected molecular clusters and nanoclusters. Isomerism in molecular MCCs is discussed within two main categories, that is, surface isomerism and core isomerism. The first Section presents some representative examples of surface isomerism involving inorganic (carbonyls and hydrides) and organic ligands, as well as isomerism due to ML fragments decorating the cluster surface. The second Section focuses on three major categories of core isomerism, that is: (1) isomers that mainly differ on M-M distances; (2) isomers displaying different structures of the metal kernels; (3) isomers possessing almost identical metal kernels and ligand shells, but differing for the positions of different types of metal atoms within the metal kernel. The third Section briefly discusses two related and very rare cases of isomerism, that is, polymerisation and coordination isomerism. General conclusions are outlined in the final Section.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268680","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}
Jan Beitlberger, Markus Ströbele, Fabian Strauß, Marcus Scheele, Carl P. Romao, Hans‐Jürgen Meyer
A metal‐rich niobium oxyiodide was prepared by soft reduction of NbI4. The structure of the new compound Nb4OI10 was determined by single‐crystal X‐ray diffraction and contains a rectangular Nb4(μ4‐O) cluster that is interconnected into layers by iodide ligands. The local structure of the Nb4OI10 cluster bears a close relationship to a defect Nb6I11 structure. The two‐dimensional van der Waals material Nb4OI8I4/2] is a small band‐gap semiconductor (<1 eV), as analysed by electrical conductivity measurements, photoresponse, experimental band gap determination, and band structure calculation.
{"title":"The Rectangular Niobium Oxyiodide Cluster Nb4OI10 – A Narrow Band‐Gap Semiconductor","authors":"Jan Beitlberger, Markus Ströbele, Fabian Strauß, Marcus Scheele, Carl P. Romao, Hans‐Jürgen Meyer","doi":"10.1002/ejic.202400329","DOIUrl":"https://doi.org/10.1002/ejic.202400329","url":null,"abstract":"A metal‐rich niobium oxyiodide was prepared by soft reduction of NbI<jats:sub>4</jats:sub>. The structure of the new compound Nb<jats:sub>4</jats:sub>OI<jats:sub>10</jats:sub> was determined by single‐crystal X‐ray diffraction and contains a rectangular Nb<jats:sub>4</jats:sub>(μ<jats:sub>4</jats:sub>‐O) cluster that is interconnected into layers by iodide ligands. The local structure of the Nb<jats:sub>4</jats:sub>OI<jats:sub>10</jats:sub> cluster bears a close relationship to a defect Nb<jats:sub>6</jats:sub>I<jats:sub>11</jats:sub> structure. The two‐dimensional van der Waals material Nb<jats:sub>4</jats:sub>OI<jats:sub>8</jats:sub>I<jats:sub>4/2</jats:sub>] is a small band‐gap semiconductor (<1 eV), as analysed by electrical conductivity measurements, photoresponse, experimental band gap determination, and band structure calculation.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250301","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}
Amino-functionalized β-diketiminate stabilized chlorogermylene 1 and chlorostannylene 2 have been prepared and structurally characterized. The reactions of 1 or 2 with KOtBu afforded the β-diketiminate stabilized tert-butoxygermylene 3 and tert-butoxystannylene 4, respectively. On the other hand, the reaction of 2 with LiN(SiMe3)2 led to the isolation of the bis-stannylene 5 containing a four-membered Sn2N2 ring. All new compounds have been characterized by multiple NMR spectroscopy and single crystal X-ray analysis.
{"title":"Synthesis and Reactivity of the Amino-Functionalized β-Diketiminate Ligand Stabilized Germylene and Stannylene","authors":"Tianyi Sun, Cheng Kong, Linlin Wu, Hao Wang","doi":"10.1002/ejic.202400378","DOIUrl":"https://doi.org/10.1002/ejic.202400378","url":null,"abstract":"Amino-functionalized β-diketiminate stabilized chlorogermylene 1 and chlorostannylene 2 have been prepared and structurally characterized. The reactions of 1 or 2 with KOtBu afforded the β-diketiminate stabilized tert-butoxygermylene 3 and tert-butoxystannylene 4, respectively. On the other hand, the reaction of 2 with LiN(SiMe3)2 led to the isolation of the bis-stannylene 5 containing a four-membered Sn2N2 ring. All new compounds have been characterized by multiple NMR spectroscopy and single crystal X-ray analysis.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250302","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}
This study presents the development of a novel planar chiral ferrocene-based NHC ligand and its corresponding metal complexes. The key unit of the imidazolium backbone, planar chiral ortho-isopropyl ferrocenyl amine, was synthesized starting from (R)-Ugi's amine. Imidazolium was obtained through the sequential condensation of glyoxal with ferrocenyl amine, followed by the ring-closure of 1,3-diferrocenyldiimine with chloromethylethyl ether. Chiral imidazolylidene NHC (IFcPr) metal complexes were prepared by treating imidazolium with silver oxide or base followed by transmetalation with appropriate metal salts. The steric and electronic properties of the IFcPr ligand were assessed using %Vbur and TEP, respectively. These assessments indicated that the ligand was as bulky as the adamantyl NHC ligand and exhibited strong donor ability similar to that of a triazolylidene NHC ligand. The catalytic performance of the copper and palladium complexes was evaluated in the asymmetric borylation of ethyl cinnamate and Suzuki–Miyaura coupling reactions, respectively. The IFcPr-Cu complex catalyzed the borylation of ethyl cinnamate with bis(pinacolato) diboron, followed by oxidation to yield the hydroxy ester with 58% yield and 30% ee. In contrast, the IFcPr-Pd-PEPPSI complex provided the axial chiral binaphthyl compound with 59% yield and 51% ee at a low catalyst loading (0.1 mol%, TON = 590).
{"title":"Synthesis, Characterization, and Catalysis of Planar Chiral Ferrocene-based N-Heterocyclic Carbene Ligands and Its Metal Complexes","authors":"Shin-ichi Fukuzawa, Shungo Shimizu, Kazuki Osawa","doi":"10.1002/ejic.202400492","DOIUrl":"https://doi.org/10.1002/ejic.202400492","url":null,"abstract":"This study presents the development of a novel planar chiral ferrocene-based NHC ligand and its corresponding metal complexes. The key unit of the imidazolium backbone, planar chiral ortho-isopropyl ferrocenyl amine, was synthesized starting from (R)-Ugi's amine. Imidazolium was obtained through the sequential condensation of glyoxal with ferrocenyl amine, followed by the ring-closure of 1,3-diferrocenyldiimine with chloromethylethyl ether. Chiral imidazolylidene NHC (IFcPr) metal complexes were prepared by treating imidazolium with silver oxide or base followed by transmetalation with appropriate metal salts. The steric and electronic properties of the IFcPr ligand were assessed using %Vbur and TEP, respectively. These assessments indicated that the ligand was as bulky as the adamantyl NHC ligand and exhibited strong donor ability similar to that of a triazolylidene NHC ligand. The catalytic performance of the copper and palladium complexes was evaluated in the asymmetric borylation of ethyl cinnamate and Suzuki–Miyaura coupling reactions, respectively. The IFcPr-Cu complex catalyzed the borylation of ethyl cinnamate with bis(pinacolato) diboron, followed by oxidation to yield the hydroxy ester with 58% yield and 30% ee. In contrast, the IFcPr-Pd-PEPPSI complex provided the axial chiral binaphthyl compound with 59% yield and 51% ee at a low catalyst loading (0.1 mol%, TON = 590).","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142268748","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}
Travis K. Deason, Gregory Morrison, Amir Mofrad, Jake Amoroso, Theodore M. Besmann, David DiPrete, Shanna L. Estes, Hans-Conrad zur Loye
Few plutonium containing silicates have been reported in the literature and only one other tetravalent plutonium silicate structure has been reported using the flux growth method. With the goal of understanding actinide incorporation into silicates, we describe herein two new plutonium (IV) silicates, Rb2PuSi6O15 and K2PuSi2O7, synthesized using a mixed alkali chloride/alkali fluoride flux growth. Both structures crystallize in the C2/c space group with lattice parameters a = 24.2980(10) Å, b = 7.1466(3) Å, c = 17.2025(8) Å and 𝛽 = 96.6560(10)o for Rb2PuSi6O15, and a = 9.9478(2) Å, b = 5.59820 (10) Å, c = 13.1848(2) Å, and 𝛽 = 105.7400(10)o for K2PuSi2O7. Comparisons to the synthesis of other reported alkali actinide silicates (Ce, U, and Th) are made. Raman spectra and DFT calculations of formation enthalpies and vibrational modes provide confirmation of structure refinements and enhanced product characterization for comparison with other materials.
{"title":"Molten Flux Synthesis of Plutonium (IV) Silicates K2PuSi2O7 and Rb2PuSi6O15","authors":"Travis K. Deason, Gregory Morrison, Amir Mofrad, Jake Amoroso, Theodore M. Besmann, David DiPrete, Shanna L. Estes, Hans-Conrad zur Loye","doi":"10.1002/ejic.202400482","DOIUrl":"https://doi.org/10.1002/ejic.202400482","url":null,"abstract":"Few plutonium containing silicates have been reported in the literature and only one other tetravalent plutonium silicate structure has been reported using the flux growth method. With the goal of understanding actinide incorporation into silicates, we describe herein two new plutonium (IV) silicates, Rb2PuSi6O15 and K2PuSi2O7, synthesized using a mixed alkali chloride/alkali fluoride flux growth. Both structures crystallize in the C2/c space group with lattice parameters a = 24.2980(10) Å, b = 7.1466(3) Å, c = 17.2025(8) Å and 𝛽 = 96.6560(10)o for Rb2PuSi6O15, and a = 9.9478(2) Å, b = 5.59820 (10) Å, c = 13.1848(2) Å, and 𝛽 = 105.7400(10)o for K2PuSi2O7. Comparisons to the synthesis of other reported alkali actinide silicates (Ce, U, and Th) are made. Raman spectra and DFT calculations of formation enthalpies and vibrational modes provide confirmation of structure refinements and enhanced product characterization for comparison with other materials.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195529","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}
Shu-Yue Xie, Bao-Han Li, Jia-Qi Li, Jiu-Jiang Dong, Xiao-Chen Ren, Bo Zhang, Jun Li, Xiao-Ying Huang
Employing metal complex cations as the structural modifiers, three new numbers of hybrid halobismuthates family, namely [NH4][Co(phen)3]BiI6 (phen = 1,10‐phenanthroline; 1), [Zn(phen)2Br][Bi(phen)Br4]·H2O (2) and [Cu(2,2'‐bipy)2Br][Cu(2,2'‐bipy)2Bi2Br9]·H2O (2,2'‐bipy = 2,2'‐bipyridine; 3) have been solvothermally constructed and structurally characterized. X‐ray crystallography analyses show that all compounds characteristic of abundant weak interactions feature the discrete anionic motifs. The obtained hybrid materials possess the semiconducting nature, with the visible light responding optical band gaps of 2.13−2.71 eV. Under the alternating light irradiation, they exhibit excellent photoelectric switching properties, whose photocurrent densities (0.85, 0.24 and 0.43 μA/cm2 for compounds 1−3, respectively) compare well with some high‐performance halobismuthate competitors. Further theoretical calculations of compound 1 reveal that the photosensitive [Co(phen)3]2+ cations contribute greatly to the bottom of conduction bands (CBs) and the top of valence bands (VBs), which may be the important reason for its excellent photoelectric behavior. The analyses of Hirshfeld surface, thermal stability and X‐ray photoelectron spectroscopy were also discussed detailedly in this paper.
{"title":"Three Metal Complex‐Decorated Halobismuthates: Syntheses, Structures, Semiconducting Behaviors and Theoretical Investigations","authors":"Shu-Yue Xie, Bao-Han Li, Jia-Qi Li, Jiu-Jiang Dong, Xiao-Chen Ren, Bo Zhang, Jun Li, Xiao-Ying Huang","doi":"10.1002/ejic.202400487","DOIUrl":"https://doi.org/10.1002/ejic.202400487","url":null,"abstract":"Employing metal complex cations as the structural modifiers, three new numbers of hybrid halobismuthates family, namely [NH4][Co(phen)3]BiI6 (phen = 1,10‐phenanthroline; 1), [Zn(phen)2Br][Bi(phen)Br4]·H2O (2) and [Cu(2,2'‐bipy)2Br][Cu(2,2'‐bipy)2Bi2Br9]·H2O (2,2'‐bipy = 2,2'‐bipyridine; 3) have been solvothermally constructed and structurally characterized. X‐ray crystallography analyses show that all compounds characteristic of abundant weak interactions feature the discrete anionic motifs. The obtained hybrid materials possess the semiconducting nature, with the visible light responding optical band gaps of 2.13−2.71 eV. Under the alternating light irradiation, they exhibit excellent photoelectric switching properties, whose photocurrent densities (0.85, 0.24 and 0.43 μA/cm2 for compounds 1−3, respectively) compare well with some high‐performance halobismuthate competitors. Further theoretical calculations of compound 1 reveal that the photosensitive [Co(phen)3]2+ cations contribute greatly to the bottom of conduction bands (CBs) and the top of valence bands (VBs), which may be the important reason for its excellent photoelectric behavior. The analyses of Hirshfeld surface, thermal stability and X‐ray photoelectron spectroscopy were also discussed detailedly in this paper.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195530","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}
Switchable molecular materials have continued to attract the interest of chemists and physicists for decades. A prominent example are spin crossover complexes, where numerous textbooks, review articles, and special issues are available. A highly interesting alternative is the coordination‐induced spin‐state switching. In this concept, we will compare the two spin‐state switching mechanisms and discuss common aspects and differences. Additionally, a short overview of coordination‐induced spin state switching will be given.
{"title":"Switching Spin‐States: Spin Crossover vs. Coordination‐Induced Spin‐State Switching","authors":"Gerald Hörner, Birgit Weber","doi":"10.1002/ejic.202400471","DOIUrl":"https://doi.org/10.1002/ejic.202400471","url":null,"abstract":"Switchable molecular materials have continued to attract the interest of chemists and physicists for decades. A prominent example are spin crossover complexes, where numerous textbooks, review articles, and special issues are available. A highly interesting alternative is the coordination‐induced spin‐state switching. In this concept, we will compare the two spin‐state switching mechanisms and discuss common aspects and differences. Additionally, a short overview of coordination‐induced spin state switching will be given.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.524,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142195531","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}
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