Polyhedron最新文献

{"title":"Structural, spectroscopic, and biological properties of an asymmetric Cu (II) Schiff-base complex: Synthesis, DNA/BSA interactions, and antimicrobial potential with experimental and computational insights","authors":"K.J. Rajimon ,&nbsp;Rafa Almeer ,&nbsp;Pooventhiran Thangaiyan ,&nbsp;Renjith Thomas","doi":"10.1016/j.poly.2024.117277","DOIUrl":"10.1016/j.poly.2024.117277","url":null,"abstract":"<div><div>A copper (II) complex with the asymmetric bidentate Schiff-base ligand (E)-2-(((4-chlorophenyl) imino) methyl) phenol was synthesized and characterized using FTIR and UV–VIS spectroscopy. Photoluminescence studies were conducted on both the copper (II) complex and the free ligand. XRD analysis revealed the copper (II) complex crystallizes in the monoclinic system, space group <em>P</em>21/<em>c</em>. The complex structure was optimized using DFT calculations with B3LYP/6-31G+(d,p) and Lanl2dz basis sets, with QTAIM and NBO analyses confirming complex formation. The energy gap of the copper (II) complex was determined to be 3.701 eV (alpha state) and 2.764 eV (beta state). MEP analysis of the optimized structure indicated a hydrophobic environment around the nitrogen atom, with the molecule exhibiting overall hydrophobicity. The chlorine atoms were identified as potential nucleophilic sites. The antimicrobial efficacy of a Schiff base copper (II) complex was evaluated against selected pathogenic bacteria (<em>B. subtilis, B. megaterum, K. pneumoniae, E. coli</em>) and the fungus <em>Candida albicans. Among these C. albicans</em> for complex showed larger zones (11–15.5 mm) at higher concentrations such as 2 and 2.5 mg/mL. Molecular docking studies suggested strong binding affinity between the complex and the target protein, this was further supported by obtained root means square deviations, root means square fluctuations, radius of gyration and hydrogen bond values during simulations. The binding free energy between BSA and the copper (II) complex was calculated as −8.7 kcal/mol, indicating significant interaction. However, only weak van der Waals interactions were observed between the complex and DNA. Toxicity studies revealed the copper (II) complex had minimal irritant effects on ocular and cutaneous tissues, with a low lethal dose. In comparison, Tricresyl phosphate showed moderate to severe ocular irritancy and modest cutaneous irritancy.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117277"},"PeriodicalIF":2.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653691","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}

{"title":"An anthryl-modified bis(terpyridine)zinc(II) complex for improved CO2 photoreduction","authors":"Lingli Shao ,&nbsp;Youting Fang ,&nbsp;Yinjun Diao ,&nbsp;Yilin Xue ,&nbsp;Shuping Cai ,&nbsp;Hui Mao ,&nbsp;Duobin Chao","doi":"10.1016/j.poly.2024.117286","DOIUrl":"10.1016/j.poly.2024.117286","url":null,"abstract":"<div><div>Transition metal complexes are an important class of molecular catalysts for CO₂ photoreduction. Herein, we report a bis(terpyridine)Zn(II) complexes modified with anthryl groups. This Zn(II) complex is highly efficient for CO₂ photoreduction with a TON of CO up to 585 and 96.2% selectivity, which is 10 times higher than that of its parent complex without any substituent modification. It is further revealed that such a significant enhancement of TON is due to the larger conjugated system of the modified Zn(II) complex, which stabilizes the proposed ligand-based radical anion. These results provide an efficient strategy to enhance the catalytic performance of a molecular catalyst by the ligand modification.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117286"},"PeriodicalIF":2.4,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653681","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}

{"title":"Coordination chemistry of a weakly coordinating carbanion","authors":"Leif Kelling,&nbsp;Viktoria H. Gessner","doi":"10.1016/j.poly.2024.117283","DOIUrl":"10.1016/j.poly.2024.117283","url":null,"abstract":"<div><div>Carbanions are typically highly reactive species but can be efficiently stabilized to even function as stable weakly coordinating anions (WCA). We now report on the coordination chemistry of the recently introduced allyl anion <strong>1</strong>, stabilized by Ar^F (Ar^F = 3,5-bis(trifluoromethyl)phenyl), triflyl substituents, with various s-block metals. A systematic crystallographic study on the s-block metal salts (Li-Cs, Ca) showed that the alkali metals have minimal impact on the anion, as indicated by the similar structural properties compared to the phosphonium salt of <strong>1</strong>. In contrast, the calcium complex showed a slightly more pronounced distortion of the allyl symmetry due to stronger Ca–O interactions with the triflyl group. Additionally, the significance of the allyl moiety in stabilizing the carbanionic charge in <strong>1</strong> was demonstrated by comparing the structural parameters and charge distribution with those of an analogous C1-anion. Overall, these studies confirm the enhanced stability of <strong>1</strong> and its weak coordination tendency.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117283"},"PeriodicalIF":2.4,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Isoniazid-Based reversible Schiff base chemosensor for Multi-Analyte (Cu2+, Ni2+, Hg2+) detection","authors":"Manpreet Kaur ,&nbsp;Virender ,&nbsp;Ashwani Kumar ,&nbsp;Santosh Kumar Dubey","doi":"10.1016/j.poly.2024.117282","DOIUrl":"10.1016/j.poly.2024.117282","url":null,"abstract":"<div><div>Isoniazid-based Schiff base N’-(furan-2-ylmethylene)isonicotinohydrazide (<strong>FINH</strong>) has been synthesized. <strong>FINH</strong> has proven its ability to selectively sense and respond to Cu²⁺, Ni²⁺, and Hg²⁺, which shows its potential as a chemosensor. UV–visible experiments, the absorption band (at 360 nm) of <strong>FINH</strong> shifted with the gradual addition of Cu²⁺, Ni²⁺, and Hg²⁺. A significant quenching in the emission band of <strong>FINH</strong> in fluorescence spectra has been observed with the addition of analytes at the physiological pH range. Cyclic voltammetric experiments have been conducted to determine the electron transfer process that occurs during the complexation of <strong>FINH</strong> with analytes. Moreover, the interactions of <strong>FINH</strong>-metal ions are reversible, and their reversible behavior has been demonstrated with the Na₂EDTA solution. The binding insights among <strong>FINH</strong> and Cu²⁺, Ni²⁺, and Hg²⁺ are explained by IR spectral study. Additionally, the <strong>FINH</strong> works within the appreciable detection limit of 9.472 x 10⁻⁷ M (for Cu²⁺), 7.685 x 10⁻⁷ M (for Ni²⁺) and 2.411 x 10⁻⁷ M (for Hg²⁺), limit of quantitation of 3.15 x 10⁻⁶ M (for Cu²⁺), 2.561 x 10⁻⁶ M (for Ni²⁺) and 8.036 x 10⁻⁷ M (for Hg²⁺). Applying this isoniazid-based reversible chemosensor in analyzing real samples demonstrates its practicality and effectiveness for multi-analyte detection. This sensor could consistently measure metal ion concentrations in various environmental and biological samples, providing a valuable tool for monitoring pollutants and evaluating exposure risks.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117282"},"PeriodicalIF":2.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142572219","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}

{"title":"Solution and solid state structures of lanthanides(III) and uranyl(II) complexes of tripodal tris(2-pyridyl)-containing ligand on Ph3P(O) platform","authors":"Anna G. Matveeva ,&nbsp;Margarita P. Pasechnik ,&nbsp;Rinat R. Aysin ,&nbsp;Tatyana V. Baulina ,&nbsp;Anna V. Vologzhanina ,&nbsp;Ivan A. Godovikov ,&nbsp;Sergey V. Matveev ,&nbsp;Igor Yu. Kudryavtsev ,&nbsp;Yuri V. Fedorov ,&nbsp;Pavel V. Dorovatovskii ,&nbsp;Mikhail E. Minyaev ,&nbsp;Valery K. Brel","doi":"10.1016/j.poly.2024.117280","DOIUrl":"10.1016/j.poly.2024.117280","url":null,"abstract":"<div><div>Reaction of tris[2-(2′-pyridylmethoxy)phenyl]phosphine oxide (<strong>L</strong>) with <em>f</em>-element nitrates resulted in 1:1 complexes. The isolated complexes of ligand <strong>L</strong> with La(III), Eu(III), Tb(III), and U(VI) nitrates, and with La(III) chloride were studied in the solid state and solution by IR, Raman, and NMR spectroscopy, X-ray analysis, and also DFT calculations. Composition and structure of the complexes vary with lanthanide cation radius. According to the data of elemental analysis, vibrational spectroscopy, and X-ray diffraction, the ligand is coordinated in tridentate mode in crystalline La(III) and solid Eu(III) complexes: [Ln(O_PO,N,O_eth-<strong>L</strong>)(H₂O)(O,O-NO₃)₃], and in monodentate mode in crystalline complex [Tb(O_PO-<strong>L</strong>)(H₂O)₂(O,O-NO₃)₃]. Nitrogen atoms of pyridine fragments of the ligand not involved in coordination produce intra- and intermolecular H-bonds with coordinated water molecules in the second coordination sphere of Ln(III). According to IR, NMR spectrometry, and DFT calculations, the structure of coordination polyhedron of the main species of Ln(III) complexes in acetonitrile solutions is retained including coordination of one of pyridine fragments in the second coordination sphere: [Ln{O_PO,N,(N*),O_eth-<strong>L</strong>}(H₂O)(O,O-NO₃)₃] and [Tb{O_PO,(N*)-<strong>L</strong>}(H₂O)₂(O,O-NO₃)₃], where Ln = La, Eu, and N* is the nitrogen atom of pyridine fragment producing intramolecular H-bond with coordinated water molecule. According IR and Raman spectroscopy, ligand <strong>L</strong> is coordinated in bidentate mode in solid complex [UO₂(O_PO,<em>N</em>-<strong>L</strong>)(O,O-NO₃)], and uncoordinated nitrogen atoms remain free. Solution structure of uranyl complex is labile and depends on solvent nature. Equilibria of complex species with variable coordination of nitrate ions, ligand <strong>L</strong>, and with probable involvement of water take place in CD₃CN and CDCl₃ solutions. Photophysical properties of the prepared Eu(III) and Tb(III) complexes were studied. The preliminary assessment of extraction properties of compound <strong>L</strong> was made. Stability of studied compounds in acetonitrile solutions was examined, and the structure of one of protolysis product of Eu(III) complex, [Eu(<strong>L</strong>H)(H₂O)(NO₃)₄], was established by micro-IR and X-ray analysis.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117280"},"PeriodicalIF":2.4,"publicationDate":"2024-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593097","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}

{"title":"Novel Cd(II) complex bearing naproxen and imidazole ligands: Synthesis, single-crystal X-ray, structural elucidation, quantum chemical investigation, molecular docking, antioxidant and antimicrobial screening","authors":"Abdulbasit Anoze Aliyu ,&nbsp;Joshua Ayoola Obaleye ,&nbsp;Abdullahi Ola Rajee ,&nbsp;Rawlings A. Timothy ,&nbsp;Favour A. Nelson ,&nbsp;Monu Joy","doi":"10.1016/j.poly.2024.117281","DOIUrl":"10.1016/j.poly.2024.117281","url":null,"abstract":"<div><div>A novel mixed ligand Cd(II) complex [Cd(nap)₂(imd)₃] bearing naproxen and imidazole ligands have been synthesized. Characterization of the mono-nuclear complex was carried out via: ¹H &amp; ¹³C NMR, FTIR, UV–vis and MS and the structure validated with SC-XRD studies. The complex forms a monoclinic crystal structure with space group <em>P</em>₂₁ and a = 13.581(8) Å, b = 8.290(5) Å, c = 16.693(10) Å, a = γ = 90°, b = 109.352(18)°,V = 1773.1(18) ų. FTIR data confirmed the binding of the naproxenato ligand via the deprotonated oxygen atom to the cadmium (II) ion. The coordination sphere around the Cd(II) center is a 7-coordinate system with a distorted pentagonal bipyramidal geometry having a CdN₃O₄ chromophore with bidentate ligation of the carboxylate ligand naproxen. Docking with the ADP-ribosyl transferase binding component protein (PDB: 6v1s) gave a binding affinity of −9.8 kcal/mol for the complex [Cd(nap)₂(imd)₃], establishing eight hydrogen bonds, with the shortest bond length observed in serine. It exhibited greater binding affinity (−9.5 kcal/mol) and established a higher number of hydrogen bonds compared to azithromycin. Tyrosine A:100 exhibited the shortest bond length among the six hydrogen bond interactions detected during docking with prostaglandin reductase 2 (PDB: 2zb7), resulting in a binding affinity of −8.6 kcal/mol. In comparison, ibuprofen demonstrated lower binding affinity (−7.6 kcal/mol) and formed fewer hydrogen bonds. Overall, molecular docking results strongly suggest that [Cd(nap)₂(imd)₃] exhibits high binding affinities with both ADP-ribosyltransferase binding component and prostaglandin reductase 2, indicating its potential as a candidate for treating bacterial infections and inflammation. The complex exhibited higher radical scavenging activity than the unbound ligands but was less than the ascorbic acid standard in the in-vitro antioxidant experiment. The complex showed promising inhibitory action against some bacterial and fungal strains. The current results may be due to the combined impact of the ligands and the metal ion during complex formation.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117281"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571759","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}

{"title":"Synthesis and characterization of Bis(imino)phosphine [NPN] ligands and their copper(I) halide complexes","authors":"Liping Chen ,&nbsp;Shuaicong Huo ,&nbsp;Piao Wang ,&nbsp;Xuyan Bai ,&nbsp;Yujia Gao ,&nbsp;Ying Yang","doi":"10.1016/j.poly.2024.117278","DOIUrl":"10.1016/j.poly.2024.117278","url":null,"abstract":"<div><div>A series of four new bis(imino)phosphine [NPN] ligands PhP(C₆H₄-2-HC=NAr)₂ (Ar = 4-OMeC₆H₄ (L¹, <strong>1</strong>), 4-ClC₆H₄ (L², <strong>2</strong>), 4-BrC₆H₄ (L³, <strong>3</strong>), 2,6-<em>i</em>Pr₂C₆H₃ (L⁴, <strong>4</strong>)) were synthesized and structurally characterized. Their reactions with Cu(I) halides CuX (X = Cl, Br, I) were explored for the assembly of coordination complexes L<em>ⁿ</em>CuX, and the effects of substituent (Ar) and anion (X) were also investigated in a comparative manner. It was found that the reaction of methoxy substituted L¹ (Ar = 4-OMeC₆H₄) with CuX gave the mononuclear Cu(I) complexes L¹CuX (X = Cl (<strong>1a</strong>), Br (<strong>1b</strong>), I (<strong>1c</strong>)) with isostructural feature. In contrast, when halogen-substituted ligands L^2-3 (4-ClC₆H₄, 4-BrC₆H₄) were applied, their reactions with CuCl afforded the formation of tetranuclear dimer [L<em>ⁿ</em>(CuCl)₂]₂ (n = 2 (<strong>2a</strong>), 3 (<strong>3a</strong>)) bridged by the Cu₂Cl₂ square, regardless of the composition of the reactants. On the other hand, reactions of L^2-3 with CuBr and CuI generated the mononuclear Cu(I) complexes L<em>ⁿ</em>CuX (n = 2, X = Br (<strong>2b</strong>), I (<strong>2c</strong>); n = 3, X = Br (<strong>3b</strong>), I (<strong>3c</strong>)) again. In all these cases above, L^1-3 ligands played the tridentate role by biting the copper(I) centers through NPN sites. When the bulky L⁴ (Ar = 2,6-<em>i</em>Pr₂C₆H₃) was involved, the binuclear dimer (L⁴CuI)₂ (<strong>4c</strong>) bridged by iodide anions was obtained, where each L⁴ ligand coordinated the copper center using the bidentate P^N mode with another imino arm pendant. In further exploration, 1,10-<em>o</em>-phenanthroline (denoted as phen) was introduced to produce the heteroleptic complex L¹CuCl(phen) (<strong>1d</strong>), where both imino arms in L¹ were pendent. The obtained ligand (L^1-4) and Cu(I) complexes were characterized by melting point, elemental analysis, FT-IR, UV–Vis, NMR, and single crystal X-ray diffraction.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117278"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561317","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}

{"title":"Bis(4-aminopyridinium) and bis(2-amino-6-methylpyridinium) cations stabilised by [MS4]2− anions: Synthesis, crystal structures, Hirshfeld surface analysis and sulfur transfer reactions","authors":"Milagrina D’Souza ,&nbsp;Nikita N. Harmalkar ,&nbsp;Vishnu R. Chari ,&nbsp;Beena K. Vernekar ,&nbsp;Sunder N. Dhuri","doi":"10.1016/j.poly.2024.117272","DOIUrl":"10.1016/j.poly.2024.117272","url":null,"abstract":"<div><div>Four new organic ammonium tetrasulfidometallates: (4-aminopyridinium)₂[MoS₄]·H₂O <strong>1</strong>, (4-aminopyridinium)₂[WS₄]·H₂O <strong>2</strong>, (2-amino-6-methylpyridinium)₂[MoS₄] <strong>3</strong>, and (2-amino-6-methylpyridinium)₂[WS₄] <strong>4</strong> have been synthesized by a well-known base promoted cation exchange method. All compounds were characterized by elemental analysis, IR/Raman/UV–Vis spectroscopy, thermogravimetric analysis, and X-ray crystallography. The structures of <strong>1</strong> and <strong>2</strong> consist of unique tetrahedral [MoS₄]²⁻ and [WS₄]²⁻ dianions, which are charge-balanced by crystallographically independent 4-aminopyridinium monocations. Additionally, both have a lattice water molecule, which contributes to the overall stability of their structures. In compounds <strong>3</strong> and <strong>4</strong>, 4-aminopyridinium of <strong>1</strong> and <strong>2</strong> are replaced by 2-amino-6-methylpyridinium cation and lack lattice water. The different H-bonding interactions <em>viz N</em><img><em>H</em>⋯<em>S</em>, <em>C</em><img><em>H</em>⋯<em>S</em>, <em>N</em><img><em>H</em>⋯<em>O</em> and <em>O</em><img><em>H</em>⋯<em>O</em> are observed in <strong>1</strong> and <strong>2</strong>, which are reduced to two <em>viz. N</em><img><em>H</em>⋯<em>S</em> and <em>C</em><img><em>H</em>⋯<em>S</em> in <strong>3</strong> and <strong>4</strong>. The weak interactions (<em>N</em><img><em>H</em>⋯<em>O</em> and <em>O</em><img><em>H</em>⋯<em>O</em>) originating from lattice water further interlink cations with [MoS₄]²⁻ and [WS₄]²⁻ anions forming extended networks in <strong>1</strong> and <strong>2</strong>. To understand the importance of intermolecular interactions in the structures of <strong>1</strong>–<strong>4</strong>, the Hirshfeld surface analyses were performed. The enrichment ratio (E) in the structures of compounds <strong>1</strong>–<strong>4</strong> was obtained. Compounds <strong>1</strong>–<strong>4</strong> were tested for their sulfur transfer ability. Only compound <strong>1</strong> showed a predominant disulfide product formation in reaction with 1,3-dibromopropane.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117272"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561316","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}

{"title":"Dichlorido(crown ether)lanthanoid(III) tetrachloroaluminate complexes","authors":"David J. Evans ,&nbsp;Zhifang Guo ,&nbsp;Glen B. Deacon ,&nbsp;Peter C. Junk","doi":"10.1016/j.poly.2024.117270","DOIUrl":"10.1016/j.poly.2024.117270","url":null,"abstract":"<div><div>Reactions between LnCl₃, AlCl₃ and a crown ether (18-crown-6 and dibenzo18-crown-6) in MeCN have led to the isolation of four new lanthanoid halide crown ether complexes, [PrCl(μ-Cl)(18-crown-6)]₂[AlCl₄]₂·2MeCN (<strong>1</strong>), [YbCl₂(18-crown-6)][AlCl₄]·MeCN (<strong>2</strong>), and [LnCl(μ-Cl)(dibenzo18-crown-6)}₂][AlCl₄]₂·6.5MeCN (Ln = La, <strong>3</strong>, Pr, <strong>4</strong>). <strong>1</strong> was also obtained by unexpected halide transfer on addition of 18-crown-6 (18C6) to MeCN solutions of [Pr(MeCN)₉][AlCl₄]₃. Complexes <strong>1</strong>, <strong>3</strong> and <strong>4</strong> have dinuclear chloride-bridged nine-coordinate cations, and <strong>2</strong> has an eight coordinate mononuclear cation.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117270"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571758","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis and characterization of uranyl complexes containing orotate and isoorotate","authors":"Emily E. Birchard ,&nbsp;Elizabeth A. Decoteau ,&nbsp;Matthew J. Polinski","doi":"10.1016/j.poly.2024.117279","DOIUrl":"10.1016/j.poly.2024.117279","url":null,"abstract":"<div><div>The synthesis and structural characterization of three new Uranyl Organic Frameworks (UOFs) – ([UO₂(C₅H₃N₂O₄)₂(H₂O)₃]·2H₂O (<strong>1</strong>), (H₃O)₃[(UO₂)₄(C₅HN₂O₄)(O)₄] (<strong>2</strong>), and H₃O[UO₂(C₅H₂N₂O₄)(OH)] (<strong>3</strong>) – in which uranyl (<span><math><mrow><mi>U</mi><msubsup><mi>O</mi><mrow><mn>2</mn></mrow><mrow><mn>2</mn><mo>+</mo></mrow></msubsup><mrow><mo>)</mo></mrow></mrow></math></span> is coordinated to either orotate (<strong>1</strong> and <strong>2</strong>) or isoorotate (<strong>3</strong>) with varying coordination modes and denticities, is presented. Complex <strong>1</strong> was prepared <em>via</em> slow evaporation from a mixed solvent (ethanol–water), while complexes <strong>2</strong> and <strong>3</strong> were prepared <em>via</em> a hydrothermal methodology. Single crystal X-ray diffraction analysis reveals that <strong>1</strong> is a 0D structure, <strong>2</strong> is a 2D structure, and <strong>3</strong> is a 1D structure. In each complex, uranium exhibits an approximately pentagonal bipyramidal geometry, a result of the linear dioxo uranyl unit being coordinated by water, orotate/isoorotate, and/or other uranyl units in the equatorial region. The observed coordination mode(s) of orotate (in <strong>1</strong>) and isoorotate (in <strong>3</strong>) are consistent with what has previously been reported. However, in complex <strong>2</strong>, the orotate ligand is bound through every possible donor atom (two carboxylate oxygens, two carbonyl oxygens, and two nitrogen atoms). This is the first example of orotate coordinated in this manner. Herein, the synthesis, characterization, and structural descriptions of these new complexes is presented.</div></div>","PeriodicalId":20278,"journal":{"name":"Polyhedron","volume":"265 ","pages":"Article 117279"},"PeriodicalIF":2.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142579002","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}