Inorganica Chimica Acta最新文献

{"title":"Tetravalent thorium and uranium complexes with cucurbit[6]uril: Direct coordination and second-shell interactions","authors":"Yingjie Zhang ,&nbsp;Stephanie Bird ,&nbsp;Thanh Ha Nguyen ,&nbsp;Inna Karatchevtseva","doi":"10.1016/j.ica.2025.122838","DOIUrl":"10.1016/j.ica.2025.122838","url":null,"abstract":"<div><div>In contrast to the well-established coordination chemistry of cucurbit[6]uril {Q[6]} with lanthanide ions, Q[6] complexes with tetravalent actinide ions are less studied and only limited to thorium(IV) ions. Herein, we report the synthesis and characterization of new Q[6] complexes with thorium(IV) and also extend to uranium(IV) ions. While complexes {[Th(H₂O)₅Cl]₂Q[6]}·2(CdCl₄)·2Cl·10H₂O (<strong>1</strong>) and {[Th(H₂O)₅Cl]₂Q[6]}·2(Ru₂O₂Cl₉)·8.666H₂O (<strong>2</strong>) were synthesized by direct reactions of thorium nitrate with Q[6] in 3 M HCl solution with the addition of CdCl₂ or RuCl₃, complexes {[U(H₂O)₅Cl]₂Q[6]}·2(ZnCl₄)·2Cl·6H₂O (<strong>3</strong>) and {U(H₂O)₉Q[6]}·2(ZnCl₄)·12.5H₂O (<strong>4</strong>) were obtained from one-pot reaction of uranyl nitrate and Q[6] in a 6 M HCl solution, with added zinc metal. Both complexes <strong>1</strong> and <strong>2</strong> contain {[Th(H₂O)₅Cl]₂Q[6]}⁶⁺ unit with two [Th(H₂O)₅Cl]³⁺ species tridentate coordinated to the two portals of Q[6] forming an unsymmetrical closed capsule. Similarly, complex <strong>3</strong> contains a {[U(H₂O)₅Cl]₂Q[6]}⁶⁺ unit with two [U(H₂O)₅Cl]³⁺ ions tridentate coordinated to the two portals of Q[6], charge balanced with (ZnCl₄)²⁻ anions. In contrast, complex <strong>4</strong> has no direct uranium bonding to Q[6], but second-shell interactions through hydrogen bonding. The roles of transition metal chloride species have been discussed. The findings help to improve the fundamental understanding of Q[6] coordination chemistry with tetravalent actinide ions especially extending to uranium(IV) ions.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122838"},"PeriodicalIF":2.7,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657209","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 ultrasensitive electrochemical sensing platform for thiamethoxam detection using novel iron-organic framework anchored graphite rod electrode","authors":"Baban Dey ,&nbsp;Km Shivangee Kushwaha ,&nbsp;SK Safdar Hossain ,&nbsp;Syed Sadiq Ali ,&nbsp;Akbar Niaz ,&nbsp;Arup Choudhury","doi":"10.1016/j.ica.2025.122832","DOIUrl":"10.1016/j.ica.2025.122832","url":null,"abstract":"<div><div>Neonicotinoids are used more frequently in agricultural seed treatments, resulting in environmental pollution and food contamination. For this end, there is a need for the development of highly reliable and effective electroanalytical platforms in such a way that obtain affordable, low-cost, and highly sensitive sensors for the determination of neonicotinoid molecules. In this experiment, our investigation testifies and characterizes the novel free-standing electrochemical sensing platform for ultrasensitive detection of thiamethoxam using an iron metal organic framework (Fe-MOF) hybrid graphite rod. Wheat-seed-like Fe/BPDCA@GRP/MOF was developed via single-step facile solvothermal treatment. In Fe/BPDCA@GRP/MOF electrode provides a large exterior area, an enormous number of pores and an abundance of active sites, which enhance absorption mechanism of thiamethoxam (TMX). This wheat-seed-like MOF hybrid GRP electrode showed superior electrochemical sensing properties and excellent electrocatalytic activity against selected analytes. Different characterization techniques were used to characterize this composite that had been developed. As-proposed electrode exhibited a lined dynamic response (LDR) from 5 to 100 μM, with lower limit of detection (LOD) of 3.44 nM, and high electroactive surface area of 0.0054 cm². Our projected electrode has successfully applied for the determination of thiamethoxam in spiked orange juice samples with acceptable recovery results varied from 98.7 % to 103.2 %. Hence, the sensor electrode offers a straightforward, budget-friendly, eco-conscious, portable, and economical solution for thiamethoxam detection.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"587 ","pages":"Article 122832"},"PeriodicalIF":2.7,"publicationDate":"2025-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144657210","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":"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>¹-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em>²-methylspiro(N/N)cyclotri-phosphazenes were obtained and their syntheses, crystal structures, spectral and thermal properties were investigated. Primarily, <em>N</em>¹-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em>²-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>), N₃P₃Cl₆ (<strong>1</strong>), with equimolar amounts of <strong>L1</strong> gave tetrachloro-<em>N</em>¹-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em>²-methylspiro(N/N)cyclotriphosphazene (<strong>2</strong>). Tetrakis(secondaryamino)-<em>N</em>¹-[(1<em>H</em>-indol-3-yl)methyl]-<em>N</em>²-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, ¹H, ¹³C and ³¹P 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 N₃P₃ rings of <strong>2a and 2d</strong> were in nearly planar and flattened boat conformations with total puckering amplitudes <em>Q</em>_<em>T</em> 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}

{"title":"Silver and selenium compounds of benzimidazolium salts containing fluorine substituents: Synthesis, characterization, and evaluation of anticancer potentials","authors":"Gülşen Karakaş ,&nbsp;Sümeyya Serin ,&nbsp;Akın Mumcu ,&nbsp;Öznur Doğan Ulu ,&nbsp;Ahmet Ulu ,&nbsp;Ali Kuruçay ,&nbsp;Burhan Ateş ,&nbsp;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 ¹H, ¹³C, ¹⁹F 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 ,&nbsp;E.V. Chernyak ,&nbsp;A.A. Ulantikov ,&nbsp;Y.M. Gaifulin ,&nbsp;V.V. Yanshole ,&nbsp;M.R. Ryzhikov ,&nbsp;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 [Re₅OsSe₈Br₆]³⁻ and [Re₄Os₂Se₈Br₆]²⁻ were synthesized and investigated. The study of the crystal structure of the Cs⁺ and Bu₄N⁺ salts of these anions showed structural similarity between bromide [Re_6-nOs_nSe₈Br₆], chloride [Re_6-nOs_nSe₈Cl₆] anions and homometallic cluster [Re₆Se₈Br₆]. Using quantum-chemical DFT calculations, it was shown that the geometry of the {Re₅Os}³⁺ and {Re₄Os₂}⁴⁺ 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 [Re₆Se₈Br₆]⁴⁻ 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}

{"title":"Red EuropiumIII complexes: Synthesis, photophysics and optoelectronics properties","authors":"Zubair Ahmed ,&nbsp;Asgar Ali ,&nbsp;Tommaso Del Rosso ,&nbsp;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^III complexes of ternary nature, [Eu(bfa)₃(L)_x] {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 dpsoCH₃ (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, ¹³C and ¹H 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,&nbsp;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}

{"title":"Electrochemical behaviour and DNA intercalation studies of novel antimicrobial Bis - Cu(II) substituted Dipyridophenazine complexes","authors":"Darren F. Beirne ,&nbsp;Sean O'’. Neill ,&nbsp;Eithne Dempsey ,&nbsp;Kevin Kavanagh ,&nbsp;Diego Seamus Montagner ,&nbsp;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. NO₂, Br, CH₃ 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}

{"title":"Synthesis, structures and magnetic properties of π-stacked supermolecular dysprosium(III) complexes with 8-hydroxyquinoline","authors":"Ying-Juan Wei,&nbsp;Yi-Cong Lou,&nbsp;Shu-Ying Luo,&nbsp;Qing-Hu Teng,&nbsp;Fu-Pei Liang,&nbsp;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^III complexes, namely, [Dy₃(ql)₈Cl(Hql)]·3CH₃OH·H₂O (<strong>1</strong>; Hql = 8-hydroxyquinoline), [Dy₃(ql)₇(NO₃)₂(Hql)]·3CH₃CN (<strong>2</strong>) and [Dy₂(ql)₃(Xa)(NO₃)₂(CH₃OH)₂(H₂O)] (<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}

{"title":"Rhenium (I) complexes based on iminopyridyl ligands: Structural, photophysical, and CO2 electrocatalytic reduction studies","authors":"Patricia M. Toro ,&nbsp;Marco Henríquez ,&nbsp;Ignacio Erazo ,&nbsp;Pedro Levín ,&nbsp;David Villaman ,&nbsp;Mirco Natali ,&nbsp;Claudio Barrientos ,&nbsp;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)₃(<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., 2021³⁾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 CO₂, showing turnover frequencies (TOFs) ranging from 8.1 to 304.4 s⁻¹.</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}