Pub Date : 2025-02-07DOI: 10.1016/j.poly.2025.117444
Guo-Ling Zhao , Bo Kong , Zhi-Guo Wang , Xiu-Fang Mo , Xiao-Yi Yi
Treatment of pyrrole-cyclometalated IrIII starting [IrIII(K2C,N-dpp)(H)(Cl)(PPh3)2] (Hdpp = 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine) and [IrIIICp*Cl2]2 in the presence of base affords binuclear IrIII–IrIII complex [IrIII (H)(Cl)(PPh3)2(μ-dpp)IrIIICp*(Cl)] (1). The structural analysis of 1 displays two IrIII centers are linked by dpp2− ligand with novel μ-(K2C,N,K2N′,N″) coordination mode. The catalytic performance of 1 for formic acid dehydrogenation in water and CO2 hydrogenation is explored.
{"title":"Synthesis, characterization and catalytic properties of binuclear IrIII–IrIII complex containing pyridylpyrrole ligand","authors":"Guo-Ling Zhao , Bo Kong , Zhi-Guo Wang , Xiu-Fang Mo , Xiao-Yi Yi","doi":"10.1016/j.poly.2025.117444","DOIUrl":"10.1016/j.poly.2025.117444","url":null,"abstract":"<div><div>Treatment of pyrrole-cyclometalated Ir<sup>III</sup> starting [Ir<sup>III</sup>(<em>K</em><sup>2</sup><sub>C,</sub><em><sub>N</sub></em>-dpp)(H)(Cl)(PPh<sub>3</sub>)<sub>2</sub>] (Hdpp = 2-[5-(pyridin-2-yl)-1H-pyrrol-2-yl]pyridine) and [Ir<sup>III</sup>Cp*Cl<sub>2</sub>]<sub>2</sub> in the presence of base affords binuclear Ir<sup>III</sup>–Ir<sup>III</sup> complex [Ir<sup>III</sup> (H)(Cl)(PPh<sub>3</sub>)<sub>2</sub>(μ-dpp)Ir<sup>III</sup>Cp*(Cl)] (<strong>1</strong>). The structural analysis of <strong>1</strong> displays two Ir<sup>III</sup> centers are linked by dpp<sup>2−</sup> ligand with novel μ-(<em>K</em><sup>2</sup><sub>C,N</sub>,<em>K</em><sup>2</sup><sub>N′,N″</sub>) coordination mode. The catalytic performance of <strong>1</strong> for formic acid dehydrogenation in water and CO<sub>2</sub> hydrogenation is explored.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117444"},"PeriodicalIF":2.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386586","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 new Ag(I) coordination compounds, namely, (imH)2[Ag2(μ-Hssal)2(H2O)2] (1), {(2mimH)2[Ag2(μ3-Hssal)2(H2O)2]}n (2) and [Ag2(µ4-Hssal)(dmim)2]n (3) with 5-sulfosalicylic acid (H3ssal) and varying imidazole derivatives (imidazole (im), 2-methylimidazole (2mim), 1,2-dimethylimidazole (dmim)) were synthesized and characterized by IR spectroscopy, elemental analysis, thermal analysis, and single crystal X-ray diffraction techniques. While imidazole and 2-methylimidazole act as counter ions outside the coordination sphere as cations by undergoing proton transfer in complexes 1 and 2, 1,2-dimethylimidazole serves as a ligand in complex 3. Complex 1 is a binuclear compound while complex 2 is two-dimensional (2D) coordination polymer, and complex 3 is one-dimensional (1D) coordination polymer. The complexes 1–3 exhibite ligand-supported argentophilic Ag⋯Ag interactions. The luminescent properties of the complexes are also discussed.
{"title":"Synthesis, characterization and luminescent properties of silver(I) complexes with 5-sulfosalicylic acid and imidazole derivatives","authors":"Eda Çavuş Kaya , Figen Arslan Biçer , Ertan Şahin , Okan Zafer Yeşilel","doi":"10.1016/j.poly.2025.117443","DOIUrl":"10.1016/j.poly.2025.117443","url":null,"abstract":"<div><div>Three new Ag(I) coordination compounds, namely, (imH)<sub>2</sub>[Ag<sub>2</sub>(μ-Hssal)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] (<strong>1</strong>), {(2mimH)<sub>2</sub>[Ag<sub>2</sub>(μ<sub>3</sub>-Hssal)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]}<sub>n</sub> (<strong>2</strong>) and [Ag<sub>2</sub>(µ<sub>4</sub>-Hssal)(dmim)<sub>2</sub>]<sub>n</sub> (<strong>3</strong>) with 5-sulfosalicylic acid (H<sub>3</sub>ssal) and varying imidazole derivatives (imidazole (im), 2-methylimidazole (2mim), 1,2-dimethylimidazole (dmim)) were synthesized and characterized by IR spectroscopy, elemental analysis, thermal analysis, and single crystal X-ray diffraction techniques. While imidazole and 2-methylimidazole act as counter ions outside the coordination sphere as cations by undergoing proton transfer in complexes <strong>1</strong> and <strong>2</strong>, 1,2-dimethylimidazole serves as a ligand in complex <strong>3</strong>. Complex <strong>1</strong> is a binuclear compound while complex <strong>2</strong> is two-dimensional (2D) coordination polymer, and complex <strong>3</strong> is one-dimensional (1D) coordination polymer. The complexes <strong>1–3</strong> exhibite ligand-supported argentophilic Ag⋯Ag interactions. The luminescent properties of the complexes are also discussed.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117443"},"PeriodicalIF":2.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143403176","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}
Pub Date : 2025-02-06DOI: 10.1016/j.poly.2025.117428
Aditya L. Shinde , Priyanka Velmurugan , Akash K. Sahoo , Shanmugam Revathi , Manickaraj Meena , Preethi Raja , Moris S. Eisen , Tapas Ghatak
Over the last hundred years, significant progress has been made in the chemistry of organo-f complexes, enhancing our understanding of their reactivity in both stoichiometric and catalytic processes. In the last three decades, there has been a significant rise in interest surrounding the electrophilic d0/fn chemistry of organo-f element complexes, attributable to their distinctive structure–reactivity relationships and remarkable efficacy in homogeneous catalysis. The influence of ligand design, encompassing electronic and steric considerations, on the catalytic efficacy of organo-f-complexes in diverse organic reactions is now broadly acknowledged. Notable progress in actinide chemistry has underscored their unique efficacy compared to lanthanides and transition metals. The stability of low-valent actinide complexes and the function of 5f orbitals in bonding and reactivity are, nevertheless, issues that continue to be extensively debated. Although actinides may share certain characteristics with transition metals in their chemical behaviors, they frequently reveal complementary or even enhanced reactivity. The increasing number of records in the Cambridge database highlights their escalating significance, facilitating more advanced chemical designs. The conventional view of actinide complexes as highly oxophilic has been limited by catalytic poisoning, which has restricted their use in oxygen-related processes. As a result, applications for these compounds have mostly found usage in cyclic ester polymerization, small-molecule activation, and hydroelementation. This review presents a comprehensive update on the synthesis, characteristics, and applications of important organoactinide complexes in organic processes. In conclusion, we present our Quo Vadis perspective, posing critical inquiries and articulating our insights regarding the future trends and advancements in this domain.
{"title":"Chemistry of uranium and thorium complexes towards challenging transformation: A recent trends","authors":"Aditya L. Shinde , Priyanka Velmurugan , Akash K. Sahoo , Shanmugam Revathi , Manickaraj Meena , Preethi Raja , Moris S. Eisen , Tapas Ghatak","doi":"10.1016/j.poly.2025.117428","DOIUrl":"10.1016/j.poly.2025.117428","url":null,"abstract":"<div><div>Over the last hundred years, significant progress has been made in the chemistry of organo-f complexes, enhancing our understanding of their reactivity in both stoichiometric and catalytic processes. In the last three decades, there has been a significant rise in interest surrounding the electrophilic d<sup>0</sup>/f<em><sup>n</sup></em> chemistry of organo-f element complexes, attributable to their distinctive structure–reactivity relationships and remarkable efficacy in homogeneous catalysis. The influence of ligand design, encompassing electronic and steric considerations, on the catalytic efficacy of organo-f-complexes in diverse organic reactions is now broadly acknowledged. Notable progress in actinide chemistry has underscored their unique efficacy compared to lanthanides and transition metals. The stability of low-valent actinide complexes and the function of 5f orbitals in bonding and reactivity are, nevertheless, issues that continue to be extensively debated. Although actinides may share certain characteristics with transition metals in their chemical behaviors, they frequently reveal complementary or even enhanced reactivity. The increasing number of records in the Cambridge database highlights their escalating significance, facilitating more advanced chemical designs. The conventional view of actinide complexes as highly oxophilic has been limited by catalytic poisoning, which has restricted their use in oxygen-related processes. As a result, applications for these compounds have mostly found usage in cyclic ester polymerization, small-molecule activation, and hydroelementation. This review presents a comprehensive update on the synthesis, characteristics, and applications of important organoactinide complexes in organic processes. In conclusion, we present our Quo Vadis perspective, posing critical inquiries and articulating our insights regarding the future trends and advancements in this domain.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117428"},"PeriodicalIF":2.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394364","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}
Pub Date : 2025-02-06DOI: 10.1016/j.poly.2025.117429
Ali Rahmatpour , Mozhgan Amiri Baramkohi
The stability of crosslinked polyacrylamide and its ability to be modified for use in a variety of applications make it an excellent support material in heterogeneous systems. Herein, we report a novel catalyst derived from copper(I)-Schiff base complex and its immobilization into crosslinked polyacrylamide which was synthesized by a two-step process, followed by the fixation of copper(I) (CPAMSL@CuI). Various techniques were used to characterize the developed polymeric copper(I) catalyst.These methods included FTIR, ICP, DR-UV–vis., FTIR, XRD, FE-SEM, EDAX, TEM, TG/DTGA, and elemental analysis. The CPAM anchored copper(I) Schiff base complex demonstrated remarkably high catalytic activity in heterogeneous three-component click reactions of alkyl or benzyl halides, sodium azide, and terminal alkynes in water at room temperature with a low catalyst loading without adding any additives yielding 1,4-disubstituted 1,2,3-triazoles without generating any waste. Furthermore, the newly developed polymeric copper(I) catalyst could be recovered and reused six consecutive times without significantly reducing the reaction yield.
{"title":"Crosslinked polyacrylamide stabilized Cu(I) catalyst for efficient synthesis of 1,2,3-triazoles via click reactions","authors":"Ali Rahmatpour , Mozhgan Amiri Baramkohi","doi":"10.1016/j.poly.2025.117429","DOIUrl":"10.1016/j.poly.2025.117429","url":null,"abstract":"<div><div>The stability of crosslinked polyacrylamide and its ability to be modified for use in a variety of applications make it an excellent support material in heterogeneous systems. Herein, we report a novel catalyst derived from copper(I)-Schiff base complex and its immobilization into crosslinked polyacrylamide which was synthesized by a two-step process, followed by the fixation of copper(I) (CPAM<sub>SL</sub>@CuI). Various techniques were used to characterize the developed polymeric copper(I) catalyst.These methods included FTIR, ICP, DR-UV–vis., FTIR, XRD, FE-SEM, EDAX, TEM, TG/DTGA, and elemental analysis. The CPAM anchored copper(I) Schiff base complex demonstrated remarkably high catalytic activity in heterogeneous three-component click reactions of alkyl or benzyl halides, sodium azide, and terminal alkynes in water at room temperature with a low catalyst loading without adding any additives yielding 1,4-disubstituted 1,2,3-triazoles without generating any waste. Furthermore, the newly developed polymeric copper(I) catalyst could be recovered and reused six consecutive times without significantly reducing the reaction yield.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117429"},"PeriodicalIF":2.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143386691","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}
Pub Date : 2025-02-06DOI: 10.1016/j.poly.2025.117438
Sampat R. Shingda , Pranali H. Hadole , Hemant M. Alone , Kailas A. More , Anirudhha Mondal , Mohd Afzal , Ajay K. Potbhare , Sudip Mondal , Nilesh V. Gandhare
Green fabrication of nanocatalyst have been used in numerous organic reactions, due to its admirable catalytical, electrical, and mechanical properties. Especially, phyto-fabrication of carbon supported nanocatalyst achieved exceptional yield with small amount of catalyst loading in organic transformations, this unique nature of catalyst based on reactivity and renewability makes this material as an efficient, outstanding, and ecofriendly nanocatalyst. In the present study, ZnFe2O4@AC nanocomposites (NCs) were synthesized by co-precipitation method using leaves extract of Careya arborea. Moreover, synthesized ZnFe2O4@AC NCs were characterized by XRD, EDS, FE-SEM and HR-TEM. The XRD reveals cubic phase with high crystallinity. While, EDS analysis confirmed elemental purity of the ZnFe2O4@AC NCs and showed the carbon blending. However, HR-TEM images shown the cubic shape with an average size in the range of 18–22 nm. The obtained ZnFe2O4@AC NCs shows catalytic properties, which is applicable for organic transformation of derivatives of Quinazolin-4(1H)-one. These Quinazolin-4(1H)-one derivatives have been accomplished with single step reaction between aromatic aldehydes and 2-aminobenzamide at room temperature. Different aromatic aldehydes substrates were used for the preparation of Quinazolin-4(1H)-one derivatives. The spectroscopic data of FT-IR, 1H NMR and 13C NMR authenticates the formation of Quinazolin-4(1H)-one derivatives. Synthetic data of derivatives demonstrated that 20 mg of catalyst loading achieved remarkable 96 % yield in ethanol. The outcomes of the prepared derivatives confirm the purity of the organic compound, which offering protocol for organic transformation have some potential features such as a simple procedure, short reaction time, mild reaction conditions, easy workup, and high yield of products.
{"title":"Phyto-fabrication and characterization of ZnFe2O4@AC nanocomposite catalyst via green pathway and its application for the synthesis of some Quinazolin-4(1H)-one derivatives","authors":"Sampat R. Shingda , Pranali H. Hadole , Hemant M. Alone , Kailas A. More , Anirudhha Mondal , Mohd Afzal , Ajay K. Potbhare , Sudip Mondal , Nilesh V. Gandhare","doi":"10.1016/j.poly.2025.117438","DOIUrl":"10.1016/j.poly.2025.117438","url":null,"abstract":"<div><div>Green fabrication of nanocatalyst have been used in numerous organic reactions, due to its admirable catalytical, electrical, and mechanical properties. Especially, phyto-fabrication of carbon supported nanocatalyst achieved exceptional yield with small amount of catalyst loading in organic transformations, this unique nature of catalyst based on reactivity and renewability makes this material as an efficient, outstanding, and ecofriendly nanocatalyst. In the present study, ZnFe<sub>2</sub>O<sub>4</sub>@AC nanocomposites (NCs) were synthesized by co-precipitation method using leaves extract of <em>Careya arborea.</em> Moreover, synthesized ZnFe<sub>2</sub>O<sub>4</sub>@AC NCs were characterized by XRD, EDS, FE-SEM and HR-TEM. The XRD reveals <em>cubic</em> phase with high crystallinity. While, EDS analysis confirmed elemental purity of the ZnFe<sub>2</sub>O<sub>4</sub>@AC NCs and showed the carbon blending. However, HR-TEM images shown the <em>cubic</em> shape with an average size in the range of 18–22 nm. The obtained ZnFe<sub>2</sub>O<sub>4</sub>@AC NCs shows catalytic properties, which is applicable for organic transformation of derivatives of Quinazolin-4(1H)-one. These Quinazolin-4(1H)-one derivatives have been accomplished with single step reaction between aromatic aldehydes and 2-aminobenzamide at room temperature. Different aromatic aldehydes substrates were used for the preparation of Quinazolin-4(1H)-one derivatives. The spectroscopic data of FT-IR, <sup>1</sup>H NMR and <sup>13</sup>C NMR authenticates the formation of Quinazolin-4(1H)-one derivatives. Synthetic data of derivatives demonstrated that 20 mg of catalyst loading achieved remarkable 96 % yield in ethanol. The outcomes of the prepared derivatives confirm the purity of the organic compound, which offering protocol for organic transformation have some potential features such as a simple procedure, short reaction time, mild reaction conditions, easy workup, and high yield of products.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117438"},"PeriodicalIF":2.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143419055","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}
Pub Date : 2025-02-04DOI: 10.1016/j.poly.2025.117430
Samuel A. Fosu , Gerra L. Licup , David C. Cantu
Complexes of gadolinium (Gd) with dodecane tetraacetic acid (DOTA) are widely used as contrasting agents in magnetic resonance imaging. However, concerns over potential toxicity to humans due to the possible unbinding of the Gd ion from the ligand has inspired research efforts into developing more stable Gd3+ chelating agents. Using molecular dynamics simulations and electronic structure calculations, we investigated the structural factors influencing the stability of Gd complexes with DOTA and DOTA-based ligands. The calculated relative binding energies, derived from all-electron single-point energy calculations, showed a strong correlation with experimental stability constants, validating the predictive ability of our computational protocol. A partial atomic charge model that considers both electrostatics and molecular polarity (CM5) showed a very strong correlation between the partial charge of the Gd ion in the complexes with experimentally measured stability constants and computationally derived binding energies, providing a simple yet effective descriptor of stability for Gd-DOTA and related complexes.
{"title":"Partial atomic charge of the ion in Gd complexes with acidic ligands can predict complex stability","authors":"Samuel A. Fosu , Gerra L. Licup , David C. Cantu","doi":"10.1016/j.poly.2025.117430","DOIUrl":"10.1016/j.poly.2025.117430","url":null,"abstract":"<div><div>Complexes of gadolinium (Gd) with dodecane tetraacetic acid (DOTA) are widely used as contrasting agents in magnetic resonance imaging. However, concerns over potential toxicity to humans due to the possible unbinding of the Gd ion from the ligand has inspired research efforts into developing more stable Gd<sup>3+</sup> chelating agents. Using molecular dynamics simulations and electronic structure calculations, we investigated the structural factors influencing the stability of Gd complexes with DOTA and DOTA-based ligands.<!--> <!-->The calculated relative binding energies,<!--> <!-->derived from all-electron single-point energy calculations,<!--> <!-->showed a strong correlation with experimental stability constants,<!--> <!-->validating the predictive ability of our computational protocol.<!--> <!-->A partial atomic charge model that considers both electrostatics and molecular polarity (CM5) showed a very strong correlation between the partial charge of the Gd ion in the complexes with experimentally measured stability constants and computationally derived binding energies,<!--> <!-->providing a simple yet effective descriptor of stability for Gd-DOTA and related complexes.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"270 ","pages":"Article 117430"},"PeriodicalIF":2.4,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143360840","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}
Pub Date : 2025-02-01DOI: 10.1016/j.poly.2024.117317
Guan Peng , Wei Xu , Fangfang Chen
In this work, in order to identify the structures of Yb-TMHD (TMHD = 2,2,6,6-tetramethyl-heptane-2,4-dionate) and Ce-TMHD in commercialized products which are usually used as the precursors of Yb/Ce-codoped silica fiber preforms, Yb(TMHD)3 (Ⅰ), Yb(TMHD)3(H2O) (Ⅱ), and Ce(TMHD)4 (Ⅲ) were synthesized. And their structures were systematically characterized by elemental analysis, nuclear magnetic resonance (NMR), Infrared spectrometry (IR), X-ray single crystal diffraction and thermogravimetric analysis (TGA). The crystal structure of a new complex Yb(TMHD)3(H2O) (Ⅱ) was confirmed: triclinic and space group P-1, a = 12.5017(5) Å, b = 13.9289(6) Å, c = 14.5519(6) Å, V = 1890.48(15) Å3. It is verified that Ce(TMHD)4 is the structure of Ce-doped organic source rather than Ce(TMHD)3 from different synthesis methods, while Yb(TMHD)3 can be the stable structure as Yb organic source. The quantum chemical calculation also confirmed the better thermodynamic stability of Yb(TMHD)3 than that of Yb(TMHD)3(H2O). The IRI calculation results verify the coordination mode and indicate that the formation of crystals is related to the interaction between ligand molecules.
{"title":"Identification of Yb and Ce complexes containing 2,2,6,6-tetramethyl-heptane-2,4-dionate ligand: Syntheses, structures and calculations","authors":"Guan Peng , Wei Xu , Fangfang Chen","doi":"10.1016/j.poly.2024.117317","DOIUrl":"10.1016/j.poly.2024.117317","url":null,"abstract":"<div><div>In this work, in order to identify the structures of Yb-TMHD (TMHD = 2,2,6,6-tetramethyl-heptane-2,4-dionate) and Ce-TMHD in commercialized products which are usually used as the precursors of Yb/Ce-codoped silica fiber preforms, Yb(TMHD)<sub>3</sub> (<strong>Ⅰ</strong>), Yb(TMHD)<sub>3</sub>(H<sub>2</sub>O) (<strong>Ⅱ</strong>), and Ce(TMHD)<sub>4</sub> (<strong>Ⅲ</strong>) were synthesized. And their structures were systematically characterized by elemental analysis, nuclear magnetic resonance (NMR), Infrared spectrometry (IR), X-ray single crystal diffraction and thermogravimetric analysis (TGA). The crystal structure of a new complex Yb(TMHD)<sub>3</sub>(H<sub>2</sub>O) (<strong>Ⅱ</strong>) was confirmed: triclinic and space group <em>P</em>-1, a = 12.5017(5) Å, b = 13.9289(6) Å, c = 14.5519(6) Å, V = 1890.48(15) Å<sup>3</sup>. It is verified that Ce(TMHD)<sub>4</sub> is the structure of Ce-doped organic source rather than Ce(TMHD)<sub>3</sub> from different synthesis methods, while Yb(TMHD)<sub>3</sub> can be the stable structure as Yb organic source. The quantum chemical calculation also confirmed the better thermodynamic stability of Yb(TMHD)<sub>3</sub> than that of Yb(TMHD)<sub>3</sub>(H<sub>2</sub>O). The IRI calculation results verify the coordination mode and indicate that the formation of crystals is related to the interaction between ligand molecules.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117317"},"PeriodicalIF":2.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098901","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}
A new hybrid complex, (C5H8N3)2[Fe (H2O)6](SO4)2·2H2O, dihydrate of bis (2,6-diaminopyridine) iron (II) sulfate, abbreviated DAPFe, was grown by slow evaporation at room temperature. It crystallizes in the orthorhombic system. The structure consists of [FeII (H2O)6]2+, 2,6-diaminopyridinium cation (C5H8N3)2+, two (SO4)2− anions, and water molecules interconnected through an extensive two-dimensional hydrogen-bond network. The stability of the supramolecular structure was maintained through hydrogen bonding interactions NH…O, OH…O and π…π interactions between the aromatic rings of the 2,6-diaminopyridine units. Hirshfeld surface analysis indicates that, among all possible molecular interactions, the O…H and H…H contacts are predominant, constituting 46.1 and 39.6 % of the total interactions in the crystal lattice, respectively. Thermal analysis (TG-DTA) confirmed the thermal stability of the crystal up to 290 °C. Infrared spectrum was recorded, validating the presence of vibrational modes corresponding to both organic and inorganic groups. Finally, the optical properties were investigated using UV–Vis absorption and photoluminescence spectroscopy, supported TDDFT theoretical calculations.
{"title":"Enhanced light and electronic properties of a dihydrate iron(II) sulfate complex with 2,6-diaminopyridinium","authors":"Oumaima Mastouri , Emna Bouaziz , Sergiu Shova , Mohamed Boujelbene","doi":"10.1016/j.poly.2024.117335","DOIUrl":"10.1016/j.poly.2024.117335","url":null,"abstract":"<div><div>A new hybrid complex, (C<sub>5</sub>H<sub>8</sub>N<sub>3</sub>)<sub>2</sub>[Fe (H<sub>2</sub>O)<sub>6</sub>](SO<sub>4</sub>)<sub>2</sub>·2H<sub>2</sub>O, dihydrate of bis (2,6-diaminopyridine) iron (II) sulfate, abbreviated <strong>DAPFe</strong>, was grown by slow evaporation at room temperature. It crystallizes in the orthorhombic system. The structure consists of [Fe<sup>II</sup> (H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup>, 2,6-diaminopyridinium cation (C<sub>5</sub>H<sub>8</sub>N<sub>3</sub>)<sup>2+</sup>, two (SO<sub>4</sub>)<sup>2−</sup> anions, and water molecules interconnected through an extensive two-dimensional hydrogen-bond network. The stability of the supramolecular structure was maintained through hydrogen bonding interactions N<img>H…O, O<img>H…O and π…π interactions between the aromatic rings of the 2,6-diaminopyridine units. Hirshfeld surface analysis indicates that, among all possible molecular interactions, the O…H and H…H contacts are predominant, constituting 46.1 and 39.6 % of the total interactions in the crystal lattice, respectively. Thermal analysis (TG-DTA) confirmed the thermal stability of the crystal up to 290 °C. Infrared spectrum was recorded, validating the presence of vibrational modes corresponding to both organic and inorganic groups. Finally, the optical properties were investigated using UV–Vis absorption and photoluminescence spectroscopy, supported TDDFT theoretical calculations.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117335"},"PeriodicalIF":2.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098907","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}
Pub Date : 2025-02-01DOI: 10.1016/j.poly.2024.117259
Kakhramon Sh. Husenov , Bako B. Umarov , Kambarali K. Turgunov , Sanat Sh. Sharipov , Bakhtiyor Sh. Ganiev , Dilshod T. Akhtamov , Damir A. Safin
A new mononuclear salt-like silver(I) complex [AgL3]NO3 (Complex 1), which was readily fabricated from 2-amino-1,3,4-thiadiazole (L), is reported. Complex 1 was analyzed by elemental analysis, FT-IR and UV–vis spectroscopy, and single crystal X-ray diffraction. Intermolecular contacts for the cation [AgL3]+ in the crystal structure of Complex 1 were examined using the Hirshfeld surface analysis. The DFT-based calculations were additionally applied to reveal electronic features of Complex 1. The molecular structure of Complex 1 exhibits a mononuclear planar cation [AgL3]+ of the triangle shape with three ligands L being monocoordinated through the thiadiazole nitrogen atom, located at the third position. Two cations [AgL3]+, which, in turn, are stabilized by three N–H⋯N hydrogen bonds, are stacked through a rich variety of noncovalent interactions formed by the thiadiazole π-system, yielding a supramolecular dimer {[AgL3]2}2+. These dimers are linked through Ag⋯Ag interactions with the formation of a 1D supramolecular cationic pillar {[AgL3]n}n+. A solution of Complex 1 in EtOH absorbs in the UV region due to intraligand transitions within L. Theoretical calculations revealed a strong electrophilic nature of the optimized structure of Complex 1.
{"title":"Synthesis, characterization and computational studies of the triangle shape complex of silver nitrate with 2-amino-1,3,4-thiadiazole","authors":"Kakhramon Sh. Husenov , Bako B. Umarov , Kambarali K. Turgunov , Sanat Sh. Sharipov , Bakhtiyor Sh. Ganiev , Dilshod T. Akhtamov , Damir A. Safin","doi":"10.1016/j.poly.2024.117259","DOIUrl":"10.1016/j.poly.2024.117259","url":null,"abstract":"<div><div>A new mononuclear salt-like silver(I) complex [AgL<sub>3</sub>]NO<sub>3</sub> (Complex <strong>1</strong>), which was readily fabricated from 2-amino-1,3,4-thiadiazole (<strong>L</strong>), is reported. Complex <strong>1</strong> was analyzed by elemental analysis, FT-IR and UV–vis spectroscopy, and single crystal X-ray diffraction. Intermolecular contacts for the cation [AgL<sub>3</sub>]<sup>+</sup> in the crystal structure of Complex <strong>1</strong> were examined using the Hirshfeld surface analysis. The DFT-based calculations were additionally applied to reveal electronic features of Complex <strong>1</strong>. The molecular structure of Complex <strong>1</strong> exhibits a mononuclear planar cation [AgL<sub>3</sub>]<sup>+</sup> of the triangle shape with three ligands <strong>L</strong> being monocoordinated through the thiadiazole nitrogen atom, located at the third position. Two cations [AgL<sub>3</sub>]<sup>+</sup>, which, in turn, are stabilized by three N–H⋯N hydrogen bonds, are stacked through a rich variety of noncovalent interactions formed by the thiadiazole π-system, yielding a supramolecular dimer {[AgL<sub>3</sub>]<sub>2</sub>}<sup>2+</sup>. These dimers are linked through Ag⋯Ag interactions with the formation of a 1D supramolecular cationic pillar {[AgL<sub>3</sub>]<em><sub>n</sub></em>}<em><sup>n</sup></em><sup>+</sup>. A solution of Complex <strong>1</strong> in EtOH absorbs in the UV region due to intraligand transitions within <strong>L</strong>. Theoretical calculations revealed a strong electrophilic nature of the optimized structure of Complex <strong>1</strong>.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117259"},"PeriodicalIF":2.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098908","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}
Pub Date : 2025-02-01DOI: 10.1016/j.poly.2024.117368
Quan-Bo Wang , Jia-Feng Gao , Fan-Ye Kong, Guo-Xu Li, Shu-Ying Luo, Kai Wang
As a kind of lanthanide complex with special molecular structures, non-symmetric binuclear lanthanide complexes ({Ln2}) feature two Ln centers with distinct coordination geometries, and have showed some unique properties that common symmetric {Ln2} could not achieved. Yet, there is still great difficult in their direct synthesis, and most of them were obtained through a serendipitous way. In this work, a series of non-symmetric {Ln2}, namely, [Ln2(bbpen)(hfac)4] [Ln = Eu (1), Tb (2) and Dy (3); H2bbpen = N, N′-bis(2-hydroxybenzyl)-N, N′-bis(2-picolyl)ethylene diamine; hfac− = 1,1,1,5,5,5-hexafluoroacetylacetonate ion], have been synthesized by a modular assembly approach successfully. This is the first application of modular assembly approach in the synthesis of non-symmetric {Ln2}. A [Ln(hfac)3(H2O)2] complex precursor and a mononuclear Ln module built by a bbpen2− ligand were assembled together by coordination substitution reaction between them, forming a kind of non-symmetric {Ln2} structure where two Ln ions featuring distinct coordination geometries are dual-bridged by two Ophenolato atoms. The fluorescence spectra of 1 and 2 show characteristic emission peaks belonging to Eu- and Tb-based transitions, respectively. In particular, 1 presents a bright red emission. The static and dynamic magnetic properties of 3 were investigated. It is revealed that 3 possesses typical dual-relaxation behavior of non-symmetric {Ln2} single molecule magnets (SMMs).
{"title":"Modular Assembly, fluorescent and magnetic properties of a series of non-symmetric binuclear lanthanide complexes","authors":"Quan-Bo Wang , Jia-Feng Gao , Fan-Ye Kong, Guo-Xu Li, Shu-Ying Luo, Kai Wang","doi":"10.1016/j.poly.2024.117368","DOIUrl":"10.1016/j.poly.2024.117368","url":null,"abstract":"<div><div>As a kind of lanthanide complex with special molecular structures, non-symmetric binuclear lanthanide complexes ({Ln<sub>2</sub>}) feature two Ln centers with distinct coordination geometries, and have showed some unique properties that common symmetric {Ln<sub>2</sub>} could not achieved. Yet, there is still great difficult in their direct synthesis, and most of them were obtained through a serendipitous way. In this work, a series of non-symmetric {Ln<sub>2</sub>}, namely, [Ln<sub>2</sub>(bbpen)(hfac)<sub>4</sub>] [Ln = Eu (<strong>1</strong>), Tb (<strong>2</strong>) and Dy (<strong>3</strong>); H<sub>2</sub>bbpen = <em>N</em>, <em>N</em>′-bis(2-hydroxybenzyl)-<em>N</em>, <em>N</em>′-bis(2-picolyl)ethylene diamine; hfac<sup>−</sup> = 1,1,1,5,5,5-hexafluoroacetylacetonate ion], have been synthesized by a modular assembly approach successfully. This is the first application of modular assembly approach in the synthesis of non-symmetric {Ln<sub>2</sub>}. A [Ln(hfac)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>] complex precursor and a mononuclear Ln module built by a bbpen<sup>2−</sup> ligand were assembled together by coordination substitution reaction between them, forming a kind of non-symmetric {Ln<sub>2</sub>} structure where two Ln ions featuring distinct coordination geometries are dual-bridged by two O<sub>phenolato</sub> atoms. The fluorescence spectra of <strong>1</strong> and <strong>2</strong> show characteristic emission peaks belonging to Eu- and Tb-based transitions, respectively. In particular, <strong>1</strong> presents a bright red emission. The static and dynamic magnetic properties of <strong>3</strong> were investigated. It is revealed that <strong>3</strong> possesses typical dual-relaxation behavior of non-symmetric {Ln<sub>2</sub>} single molecule magnets (SMMs).</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"267 ","pages":"Article 117368"},"PeriodicalIF":2.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098523","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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