{"title":"Indolyl-3-spiro(N/N)cyclotriphosphazenes: syntheses, spectral, crystallographic and thermal analyses","authors":"Arzu Binici","doi":"10.1016/j.ica.2025.122836","DOIUrl":"10.1016/j.ica.2025.122836","url":null,"abstract":"<div><div>In this study, tetrakis(secondaryamino)-<em>N</em><sup>1</sup>-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em><sup>2</sup>-methylspiro(N/N)cyclotri-phosphazenes were obtained and their syntheses, crystal structures, spectral and thermal properties were investigated. Primarily, <em>N</em><sup>1</sup>-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em><sup>2</sup>-methyl-1,2-diaminoethane (<strong>L1</strong>) was synthesized from the reaction of indole-3-carboxaldehyde and <em>N</em>-methyl-1,2-diaminoethane in the equimolar ratio 1:1. Reactions of hexachlorocyclotriphosphazene (<strong>HCCP</strong>), N<sub>3</sub>P<sub>3</sub>Cl<sub>6</sub> (<strong>1</strong>), with equimolar amounts of <strong>L1</strong> gave tetrachloro-<em>N</em><sup>1</sup>-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em><sup>2</sup>-methylspiro(N/N)cyclotriphosphazene (<strong>2</strong>). Tetrakis(secondaryamino)-<em>N</em><sup>1</sup>-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em><sup>2</sup>-methylspiro(N/N)cyclotriphosphazenes (<strong>2a-2d</strong>) were prepared from the condensation reactions of spiro <strong>2</strong> with an excess of pyrrolidine, piperidine, morpholine and 1,4-dioxa-8-azaspiro[4,5]decane (DASD), respectively, The structures of the new products <strong>L1, 2</strong> and <strong>2a–2d</strong> were proven by microanalysis, HRMS, FTIR, HSQC, <sup>1</sup>H, <sup>13</sup>C and <sup>31</sup>P data. The molecular and crystal structures of <strong>2a</strong> and <strong>2d</strong> were evaluated by single crystal X-ray crystallography. The six-membered N<sub>3</sub>P<sub>3</sub> rings of <strong>2a and 2d</strong> were in nearly planar and flattened boat conformations with total puckering amplitudes <em>Q</em><sub><em>T</em></sub> of 0.0419 (14) Å (<strong>2a</strong>) and 0.1192 (23) Å (<strong>2d</strong>). In addition, the thermal characterizations of the new phosphazenes are evaluated by <strong>TG</strong> and <strong>DTA</strong> techniques. The limited oxygen index (<strong>LOI</strong>) parameters of the compounds were determined from the TGA data to determine their oxidation resistance values. The values found are in the range of 28.4–31.6, indicating that these compounds are in the group of self-extinguishing materials.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122836"},"PeriodicalIF":2.7,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144614687","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}
Gülşen Karakaş , Sümeyya Serin , Akın Mumcu , Öznur Doğan Ulu , Ahmet Ulu , Ali Kuruçay , Burhan Ateş , Ali Erdoğan
{"title":"Silver and selenium compounds of benzimidazolium salts containing fluorine substituents: Synthesis, characterization, and evaluation of anticancer potentials","authors":"Gülşen Karakaş , Sümeyya Serin , Akın Mumcu , Öznur Doğan Ulu , Ahmet Ulu , Ali Kuruçay , Burhan Ateş , Ali Erdoğan","doi":"10.1016/j.ica.2025.122833","DOIUrl":"10.1016/j.ica.2025.122833","url":null,"abstract":"<div><div>The applications of fluorine in the field of drug design are expanding at a rapid pace. The development of synthetic methodologies has enabled the creation of new fluorinated motifs. Benzimidazolium salts represent a significant source of N-heterocyclic carbenes (NHCs), a distinctive class of ligands. These salts have a wide range of applications due to their notable qualities. The present study encompasses the synthesis of four novel benzimidazolium salts (<strong>1a-d</strong>) substituted with 2,6-difluorobenzyl moiety. Subsequently, the prepared salts were utilized in the synthesis of silver complexes (<strong>2a-d</strong>) and selenium compounds (<strong>3a-d</strong>). The structures of all compounds were elucidated by <sup>1</sup>H, <sup>13</sup>C, <sup>19</sup>F NMR, HRMS, FT-IR spectroscopies, and elemental analysis techniques. The incorporation of a fluorine atom into the molecular structure of a compound has been known to induce substantial alterations in the biological responses of mentioned compound. Therefore, the cytotoxic effect of these compounds was also evaluated using the MTT assay on HCT116 and L929 cell lines. Acridine orange (AO)/ethidium bromide (EB) staining were used for the detection of apoptosis. Notably, cytotoxicity assays showed that compound <strong>3d</strong> displayed approximately 22-fold higher potency against HCT116 than cisplatin. Taken together, this enhanced efficacy signifies the promising role of silver and selenium compounds of benzimidazolium salts containing fluorine substituents in anticancer therapies.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122833"},"PeriodicalIF":2.7,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144604852","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":"Heterometallic octahedral clusters [Re6-nOsnSe8Br6](4-n)– (n = 1, 2): systematic change of the oxidation potential by non-isovalent metal substitution","authors":"V.K. Gaifulina , E.V. Chernyak , A.A. Ulantikov , Y.M. Gaifulin , V.V. Yanshole , M.R. Ryzhikov , N.G. Naumov","doi":"10.1016/j.ica.2025.122835","DOIUrl":"10.1016/j.ica.2025.122835","url":null,"abstract":"<div><div>Compounds based on new heterometallic cluster anions [Re<sub>5</sub>OsSe<sub>8</sub>Br<sub>6</sub>]<sup>3−</sup> and [Re<sub>4</sub>Os<sub>2</sub>Se<sub>8</sub>Br<sub>6</sub>]<sup>2−</sup> were synthesized and investigated. The study of the crystal structure of the Cs<sup>+</sup> and Bu<sub>4</sub>N<sup>+</sup> salts of these anions showed structural similarity between bromide [Re<sub>6-n</sub>Os<sub>n</sub>Se<sub>8</sub>Br<sub>6</sub>], chloride [Re<sub>6-n</sub>Os<sub>n</sub>Se<sub>8</sub>Cl<sub>6</sub>] anions and homometallic cluster [Re<sub>6</sub>Se<sub>8</sub>Br<sub>6</sub>]. Using quantum-chemical DFT calculations, it was shown that the geometry of the {Re<sub>5</sub>Os}<sup>3+</sup> and {Re<sub>4</sub>Os<sub>2</sub>}<sup>4+</sup> metal centers is close to an undistorted octahedron. It has been also found that the non-isovalent substitution of rhenium atoms by osmium resulted in the stabilization of the cluster's highest occupied molecular orbitals (HOMOs) by about 0.7 eV <em>per Os</em> atom. This effect was confirmed experimentally by cyclic voltammetry: a strong anodic shift of the oxidation potential of the new anions with respect to the homometallic cluster [Re<sub>6</sub>Se<sub>8</sub>Br<sub>6</sub>]<sup>4−</sup> was demonstrated.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122835"},"PeriodicalIF":2.7,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657207","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}
Zubair Ahmed , Asgar Ali , Tommaso Del Rosso , Shafat Ahmad Khan
{"title":"Red EuropiumIII complexes: Synthesis, photophysics and optoelectronics properties","authors":"Zubair Ahmed , Asgar Ali , Tommaso Del Rosso , Shafat Ahmad Khan","doi":"10.1016/j.ica.2025.122831","DOIUrl":"10.1016/j.ica.2025.122831","url":null,"abstract":"<div><div>In this article, four Eu<sup>III</sup> complexes of ternary nature, [Eu(bfa)<sub>3</sub>(L)<sub>x</sub>] {L = diphenyl sulphoxide (dpso) (<strong>1</strong>), dpsoCl (bis(4-chlorophenyl) sulphoxide) (<strong>3</strong>) and tppo (triphenylphosphine oxide) (x = 2) (<strong>4</strong>), and dpsoCH<sub>3</sub> (4,4′-dimethyldiphenylsulfoxide) (x = 3) (<strong>2</strong>)}, bfa = 4,4,4-Trifluoro-1-phenyl-1,3-butanedione}, were synthesised and thoroughly characterized. The structures of the complexes were confirmed by FTIR, <sup>13</sup>C and <sup>1</sup>H NMR analyses. The Sparkle model/PM7 analysis shows that the complexes possess structural geometries as: <strong>1</strong> and <strong>4</strong> – Biaugmented trigonal prism, <strong>3 –</strong>square antiprism, and <strong>2</strong> –spherical capped square antiprism. The complexes exhibit red luminescence with a photoluminescence quantum yields ranging from 32 to 61 %. The presence of co-ligands in the complexes significantly increases the photophysical parameters, particularly in the solid state. The energy transfer rates and back energy transfer rates of the complexes are determined. The complexes showed pure red emissions with CIE color coordinates as x = 0.66 and y = 0.33 (612 nm), suggesting their possible use as red component in organic light emitting devices (OLEDs). In particular, complex <strong>4</strong> exhibits the highest efficiency and stability. As a result, this complex– as an emiiting component– was tested in an OLED with a multiple layer structure.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122831"},"PeriodicalIF":2.7,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144633421","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":"Unveiling the potential of luminescent metal–organic frameworks as optical sensors for the detection of food contaminants","authors":"Imtiyaz Ahmad Lone, Jigneshkumar V. Rohit","doi":"10.1016/j.ica.2025.122830","DOIUrl":"10.1016/j.ica.2025.122830","url":null,"abstract":"<div><div>Food toxicity has become an increasing concern due to the rising levels of contaminants in food products. The identification of foodborne toxins is crucial for safeguarding public health and ensuring food safety. In recent decades, advances in sensor technology have enabled the rapid, efficient, and reliable detection of food pollutants. Metal–organic frameworks (MOFs) have garnered significant attention as efficient sensory materials due to their active metal sites, large surface areas, excellent chemical and thermal stability, and tunable structures with variable pore sizes, making them a promising alternative to conventional analytical techniques. However, despite extensive research on MOFs for contaminant detection, there is a notable lack of studies dedicated specifically to luminescent MOF-based optical sensors for food contaminants. This review comprehensively discusses the latest advancements in the design and development of luminescent MOFs based optical sensors, focusing on their synthesis routes—including solvothermal, mechanochemical, sonochemical, and electrochemical methods—and the strategies employed to induce and tune their luminescence, such as ligand-based, metal-based, guest-induced, and exciplex emission. Special attention is given to their working mechanisms and their applications for the detection of wide spectrum of food contaminants, including veterinary drug residues, heavy metals, pesticides, microbial pathogens, illegal additives, and other hazardous substances. Challenges such as stability, scalability, and regulatory concerns are critically analyzed, along with future perspectives that emphasize integration with the real-time monitoring platforms. This work aims to serve as a foundational resource for researchers and stakeholders developing next-generation sensors for enhanced food safety and public health protection.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122830"},"PeriodicalIF":2.7,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144570694","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}
Darren F. Beirne , Sean O'’. Neill , Eithne Dempsey , Kevin Kavanagh , Diego Seamus Montagner , Stephen Barrett
{"title":"Electrochemical behaviour and DNA intercalation studies of novel antimicrobial Bis - Cu(II) substituted Dipyridophenazine complexes","authors":"Darren F. Beirne , Sean O'’. Neill , Eithne Dempsey , Kevin Kavanagh , Diego Seamus Montagner , Stephen Barrett","doi":"10.1016/j.ica.2025.122829","DOIUrl":"10.1016/j.ica.2025.122829","url":null,"abstract":"<div><div>The public health threat caused by antimicrobial drug resistance has led to research towards alternatives to current chemotherapeutics, with metal-based complexes providing an excellent and promising avenue. Cu(II) species are of particular interest in this area due to their redox properties that could interfere with and inhibit bacterial growth. Here, we report the synthesis and characterisation of four novel bis-Cu(II) substituted Dipyridophenazine complexes. The dypyridophenazine ligands (DPPZ) where synthesized with different substituents at the 11 position (i.e. NO<sub>2</sub>, Br, CH<sub>3</sub> and CN) to evaluate the effect of the functionality with respect the redox and biological behaviour. The DNA intercalation properties together with a detailed electrochemical study of the complexes and of the ligands is reported. The toxicity of the complexes against Methicillin Resistant <em>Staphylococcus aureus</em> (MRSA) and the yeast <em>Candida albicans</em> was characterised and the promise of this family of complexes as novel anti-microbial drugs in a post-antibiotic age was demonstrated.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122829"},"PeriodicalIF":2.7,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144522098","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}
Ying-Juan Wei, Yi-Cong Lou, Shu-Ying Luo, Qing-Hu Teng, Fu-Pei Liang, Kai Wang
{"title":"Synthesis, structures and magnetic properties of π-stacked supermolecular dysprosium(III) complexes with 8-hydroxyquinoline","authors":"Ying-Juan Wei, Yi-Cong Lou, Shu-Ying Luo, Qing-Hu Teng, Fu-Pei Liang, Kai Wang","doi":"10.1016/j.ica.2025.122828","DOIUrl":"10.1016/j.ica.2025.122828","url":null,"abstract":"<div><div>In this work, we report three Dy<sup>III</sup> complexes, namely, [Dy<sub>3</sub>(ql)<sub>8</sub>Cl(Hql)]·3CH<sub>3</sub>OH·H<sub>2</sub>O (<strong>1</strong>; Hql = 8-hydroxyquinoline), [Dy<sub>3</sub>(ql)<sub>7</sub>(NO<sub>3</sub>)<sub>2</sub>(Hql)]·3CH<sub>3</sub>CN (<strong>2</strong>) and [Dy<sub>2</sub>(ql)<sub>3</sub>(Xa)(NO<sub>3</sub>)<sub>2</sub>(CH<sub>3</sub>OH)<sub>2</sub>(H<sub>2</sub>O)] (<strong>3</strong>, HXa = xanthene-9-carboxylic acid). Both <strong>1</strong> and <strong>2</strong> feature quasi-linear trinuclear cluster structures, while <strong>3</strong> has a dinuclear structure. Significantly, diverse intermolecular π-π interactions led to the structural variety in three systems, forming supermolecular dimers of <strong>1</strong> and <strong>3</strong>, and a supramolecular 2D honeycomb-like framework of <strong>2</strong>. Magnetic studies demonstrate that <strong>1</strong> and <strong>3</strong> exhibit field induced dual relaxation behavior. The efficient energy barriers for their slow relaxation processes are only 3.0 and 2.1 K. In contrast, <strong>2</strong> displays zero-field relaxation behavior, with an efficient energy barrier of 140 K. This work highlights how ligand field engineering and π-π stacking interactions synergistically modulate relaxation dynamics in lanthanoid single-molecule magnets systems.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122828"},"PeriodicalIF":2.7,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144534235","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}
Patricia M. Toro , Marco Henríquez , Ignacio Erazo , Pedro Levín , David Villaman , Mirco Natali , Claudio Barrientos , Alan R. Cabrera
{"title":"Rhenium (I) complexes based on iminopyridyl ligands: Structural, photophysical, and CO2 electrocatalytic reduction studies","authors":"Patricia M. Toro , Marco Henríquez , Ignacio Erazo , Pedro Levín , David Villaman , Mirco Natali , Claudio Barrientos , Alan R. Cabrera","doi":"10.1016/j.ica.2025.122827","DOIUrl":"10.1016/j.ica.2025.122827","url":null,"abstract":"<div><div>Five rhenium complexes [Re(CO)<sub>3</sub>(<em>N,N</em>)Cl] (<strong>C1–5</strong>), in which <em>N,N</em> represents iminopyridyl ligands, were successfully synthesized. The structural characterization of these compounds includes NMR, FT-IR, and HRMS analyses. Additionally, the molecular structures of <strong>C2</strong> and <strong>C3</strong> were determined through X-ray diffraction analysis. Electrochemical characterization indicates a metal-centered HOMO and a ligand-centered LUMO, with the latter strongly influenced by the nature of the substituent. The photophysical properties of all complexes were examined using UV–Vis spectroscopy and spectrofluorometric measurements in dichloromethane solution at room temperature, as well as in the solid state. All complexes exhibit a spin-allowed MLCT absorption transition in the 405–471 nm range. In degassed dichloromethane solution at room temperature, complexes <strong>C1–3</strong> and <strong>C5</strong> display an unstructured (Kinzel et al., 2021<sup>3)</sup>MLCT emission in the red region of the visible spectrum. In contrast, complex <strong>C4</strong>, which features the lower-energy absorption, is nearly non-luminescent. Conversely, all complexes show emission in the solid state, with bands presenting a distinctive hypsochromic shift characteristic of MLCT states. Finally, all compounds were evaluated for their ability to promote the electrocatalytic reduction of CO<sub>2</sub>, showing turnover frequencies (TOFs) ranging from 8.1 to 304.4 s<sup>−1</sup>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122827"},"PeriodicalIF":2.7,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144518832","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}
Francesco Rossi , Gianmarco Stati , Thithawat Trakoolwilaiwan , Nguyen Thi Kim Thanh , Silvia Sancilio , Roberta Di Pietro
{"title":"Preliminary study on ex vivo efficacy of curcumin‑silver nanoparticles as a treatment of human pterygium-derived keratinocytes","authors":"Francesco Rossi , Gianmarco Stati , Thithawat Trakoolwilaiwan , Nguyen Thi Kim Thanh , Silvia Sancilio , Roberta Di Pietro","doi":"10.1016/j.ica.2025.122826","DOIUrl":"10.1016/j.ica.2025.122826","url":null,"abstract":"<div><div>Pterygium is a progressive disease of the human eye in which an invasive growth arises from the sub-conjunctival tissue and extends onto the cornea, eventually reaching the pupil and compromising visual function. This disease is commonly diffused in human population living in the tropical region with an average incidence of 7 % of cases in India, Singapore and China and peaks of 30 % in Japan. The available surgical or pharmacological treatments are only partially successful in stopping the disease and imply a great risk of aggressive relapse. The proposed inorganic nanoparticles conjugated with curcumin have demonstrably been able to reduce of 30 % ± 0.2 % the vitality of pterygium keratinocytes extracted by affected patients, thus offering an alternative therapeutic option for the containment of this human disease.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122826"},"PeriodicalIF":2.7,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144365987","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}
Steven Arnold , John Bacsa , Christian Jelsch , Nicholas C. Thomas
{"title":"Synthesis, crystal structure, spectral properties, and charge density analysis of 4-coordinate Bis[1-(4-N,N-dimethylaminophenyl)-1,3-butadionato-O,O′]copper(II)1","authors":"Steven Arnold , John Bacsa , Christian Jelsch , Nicholas C. Thomas","doi":"10.1016/j.ica.2025.122824","DOIUrl":"10.1016/j.ica.2025.122824","url":null,"abstract":"<div><div>The reaction of 1-[4-(dimethylamino)phenyl]-1,3-butanedione (Hdapb) with copper(II) chloride produces bis[1-(4-<em>N</em>,<em>N</em>-dimethylaminophenyl)-1,3-butadionato-O,O′]copper(II), Cu(dapb)<sub>2</sub> (<strong>I</strong>), with high yields. The title compound crystallizes exceptionally well, forming suitable crystals for X-ray crystallography and detailed electron distribution studies for copper. The copper atom can be treated as an isolated 4-coordinate atom with a single unpaired 3d electron. Contrary to expectations, the two dapb ligands bonded to the copper are inequivalent, characterized by unequal Cu<img>O bond lengths. A suitable model confirming the correct d-electron splitting and distortion of this d<sup>9</sup>-distorted square planar complex and establishing its spectral properties is proposed. <em>R</em>-free calculations were carried out to determine the optimal weighting parameters for the chemical equivalence and local symmetry restraints on the charge density. The charge density confirms the appropriate d-electron splitting for a distorted d<sup>9</sup>-square planar complex and establishes its compatibility with the complex's spectral properties. The UV–visible absorption spectra show a charge transfer band in addition to the expected d-d bands, whose energies deviate from the trend previously documented in the literature.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122824"},"PeriodicalIF":2.7,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144518831","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}