Inorganica Chimica Acta最新文献

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Defect-engineered UiO-66-NH2 (AO)-3: Achieving enhanced fluorescence sensing of uranyl ions
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-17 DOI: 10.1016/j.ica.2025.122655
Shi-Qi Li , Hong-Bo Peng , Xiao-Hong Cao , Zhi-Min Dong , You-Qun Wang , Zhi-Bin Zhang , Yun-Hai Liu
{"title":"Defect-engineered UiO-66-NH2 (AO)-3: Achieving enhanced fluorescence sensing of uranyl ions","authors":"Shi-Qi Li ,&nbsp;Hong-Bo Peng ,&nbsp;Xiao-Hong Cao ,&nbsp;Zhi-Min Dong ,&nbsp;You-Qun Wang ,&nbsp;Zhi-Bin Zhang ,&nbsp;Yun-Hai Liu","doi":"10.1016/j.ica.2025.122655","DOIUrl":"10.1016/j.ica.2025.122655","url":null,"abstract":"<div><div>Advances in nuclear technology have accentuated the imperative of uranyl ions (UO<sub>2</sub><sup>2+</sup>) monitoring in aquatic ecosystems, due to their significant environmental and health repercussions. Metal–Organic Frameworks (MOFs), celebrated for their tunable porosity and substantial surface area, offer a promising platform for enhancing analytical detection capabilities. Empirical evidence from recent scholarly work indicates that defect engineering within MOFs can significantly improve their physicochemical properties, encompassing sensing performance. In this study, the fluorescence behavior of UiO-66-NH<sub>2</sub> (Zr-MOF) was successfully modulated through the deliberate incorporation of defects, which reduced the exciton dissociation energy and subsequently increased fluorescence emission efficiency. Additionally, the introduction of engineered defects engendered a more permeable structure, which facilitated the rapid entry and enrichment of UO<sub>2</sub><sup>2+</sup> within the internal cavities, consequently promoting a pronounced fluorescence quenching response. The synergistic effects of defect modulation and amidoxime functionalization endowed UiO-66-NH<sub>2</sub>(AO)-3 with enhanced detection sensitivity and selectivity for UO<sub>2</sub><sup>2+</sup>, realizing a detection limit as low as 24.6 nmol·L<sup>−1</sup> (12.4 ppb), indicative of its robust signal amplification capacity for the trace detection of UO<sub>2</sub><sup>2+</sup>. Our findings proffer a novel approach to enhance the sensing capabilities of MOFs, contributing a sensitive and selective analytical technique for the detection of UO<sub>2</sub><sup>2+</sup>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122655"},"PeriodicalIF":2.7,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643426","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}
引用次数: 0
An expedition towards designing of luminescent supramolecular metallogels for chemosensing applications
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-14 DOI: 10.1016/j.ica.2025.122635
Rubi Moral, Gopal Das
{"title":"An expedition towards designing of luminescent supramolecular metallogels for chemosensing applications","authors":"Rubi Moral,&nbsp;Gopal Das","doi":"10.1016/j.ica.2025.122635","DOIUrl":"10.1016/j.ica.2025.122635","url":null,"abstract":"<div><div>Luminescent supramolecular metallogels have gained significant attention in the past decade as chemosensors for various biologically and environmentally important analytes. Their impressive optical properties and dynamic metal-ligand bonds give these luminescent metallogels a stimuli-responsive behavior. By carefully designing the receptor system and selecting the appropriate metal ion, it is possible to create function-oriented metallogel systems. This review emphasizes the chemosensing capabilities of luminescent metallogels and their potential for use as functional soft materials in real-life applications.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122635"},"PeriodicalIF":2.7,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143643425","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}
引用次数: 0
Trans-Pd(II) complexes: A different approach for the development of promising anticancer drugs
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-12 DOI: 10.1016/j.ica.2025.122645
Ester Giorgi , Francesca Binacchi , Michele Mannelli , Damiano Cirri , Andrea Cesari , Matteo Boldrini , Carlo Marotta , Claudia Ghelarducci , Diletta Corvaglia , Fabio Bellina , Tania Gamberi , Alessandro Pratesi , Chiara Gabbiani
{"title":"Trans-Pd(II) complexes: A different approach for the development of promising anticancer drugs","authors":"Ester Giorgi ,&nbsp;Francesca Binacchi ,&nbsp;Michele Mannelli ,&nbsp;Damiano Cirri ,&nbsp;Andrea Cesari ,&nbsp;Matteo Boldrini ,&nbsp;Carlo Marotta ,&nbsp;Claudia Ghelarducci ,&nbsp;Diletta Corvaglia ,&nbsp;Fabio Bellina ,&nbsp;Tania Gamberi ,&nbsp;Alessandro Pratesi ,&nbsp;Chiara Gabbiani","doi":"10.1016/j.ica.2025.122645","DOIUrl":"10.1016/j.ica.2025.122645","url":null,"abstract":"<div><div>Pd(II) complexes, thanks to the similarity of their coordination chemistry to that of Pt(II) compounds and their improved solubility in water than the latter, offer a promising way for the design of novel anticancer agents. Considering that <em>trans</em>-Pd(II) complexes are more cytotoxic than their <em>cis</em>-counterparts and endowing them with ligands that could grant them improved stabilization during their circulation inside the body, a panel of <em>trans</em>-Pd(II) complexes with general formula <em>trans</em>-PdL<sub>2</sub>X<sub>2</sub> (where L = pyridine or piperidine, X = Cl, Br, I) was synthesized. The interactions of these complexes with model proteins were studied with UV–vis and NMR spectroscopy, and their <em>in vitro</em> activity against selected cancer cell lines was also investigated. The study demonstrates that square-planar trans-Pd(II) complexes have potential as chemical tools in medicinal chemistry. They are able to interact with proteomic targets, and despite their limited cytotoxic activity towards the selected tumor cell lines, the interaction profiles and solution reactivity provide valuable mechanistic insights on the mode of action of this class of compounds. Indeed, a reproducible and accessible methodology was defined to investigate the square-planar <em>trans</em>-Pd(II) complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122645"},"PeriodicalIF":2.7,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620632","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}
引用次数: 0
Crystal structure, thermal and luminescent properties of the complex of zinc(II) acrylate and 4′-phenyl-2,2′:6′,2″-terpyridine
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-12 DOI: 10.1016/j.ica.2025.122649
Rose K. Baimuratova , Evgeny S. Sorin , Denis V. Korchagin , Lavrenty G. Gutsev , Gennadii V. Shilov , Vladimir A. Zhinzhilo , Igor E. Uflyand , Alexander V. Akkuratov , Gulzhian I. Dzhardimalieva
{"title":"Crystal structure, thermal and luminescent properties of the complex of zinc(II) acrylate and 4′-phenyl-2,2′:6′,2″-terpyridine","authors":"Rose K. Baimuratova ,&nbsp;Evgeny S. Sorin ,&nbsp;Denis V. Korchagin ,&nbsp;Lavrenty G. Gutsev ,&nbsp;Gennadii V. Shilov ,&nbsp;Vladimir A. Zhinzhilo ,&nbsp;Igor E. Uflyand ,&nbsp;Alexander V. Akkuratov ,&nbsp;Gulzhian I. Dzhardimalieva","doi":"10.1016/j.ica.2025.122649","DOIUrl":"10.1016/j.ica.2025.122649","url":null,"abstract":"<div><div>In this work, the structure of a bifunctional metal-containing monomer of zinc acrylate (Acr) and 4′-phenyl-2,2′:6′,2″-terpyridine (PhTpy), which is used in the synthesis of self-healing polymers, is characterized for the first time. The planar structure and electron distribution in the terpyridine moieties are responsible for an extensive network of non-covalent interactions that occur during the packing of the structure, as well as for the luminescent properties. The complex was characterized using a number of physicochemical methods, such as elemental, thermogravimetric, single-crystal X-ray analysis, X-ray diffraction analysis, IR and DSC spectroscopy. The kinetic approaches were used to elucidate the thermal transformations of the obtained monomer. In addition, the activation energy of solid-state polymerization, which is attributed to the primary cleavage of the M–O bond in the carboxyl group, was estimated using two independent methods.</div><div>The complex is formulated as a co-crystalizate Zn(Acr)<sub>2</sub>PhTpy × ZnAcrClPhTpy with a solvated water molecule. Each zinc ion is coordinated by three nitrogen atoms of the PhTpy and either two oxygen atoms of the acrylate anions or one oxygen atom of the acrylate and chloride anions and has a distorted trigonal-bipyramidal coordination environment characteristic for PhTpy transition metal complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122649"},"PeriodicalIF":2.7,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627971","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}
引用次数: 0
Two 2D coordination polymers derived from 1-(2-carboxyethyl)-4,4′-bipyridinium bromide: Photochromism
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-11 DOI: 10.1016/j.ica.2025.122648
Guozheng Zhao, Jinjian Liu
{"title":"Two 2D coordination polymers derived from 1-(2-carboxyethyl)-4,4′-bipyridinium bromide: Photochromism","authors":"Guozheng Zhao,&nbsp;Jinjian Liu","doi":"10.1016/j.ica.2025.122648","DOIUrl":"10.1016/j.ica.2025.122648","url":null,"abstract":"<div><div>We synthesized and structurally analyzed two new two-dimensional (2D) viologen coordination polymers, [Cd(CBbpy)(<em>p</em>-BDC)·H<sub>2</sub>O]<sub>n</sub> (<strong>1</strong>) and [Co<sub>2</sub>(CBbpy)<sub>2</sub>(<em>m</em>-BDC)(H<sub>2</sub>O)<sub>4</sub>·0.5(<em>m</em>-BDC)·2H<sub>2</sub>O]<sub>n</sub> (<strong>2</strong>), which originate from 1-(2-carboxyethyl)-4,4′-bipyridinium bromide (HCBbpyBr). Single-crystal X-ray diffraction analysis shows that compound <strong>1</strong> crystallizes within the monoclinic space group <em>P</em>2<sub>1</sub>/n, whereas compound <strong>2</strong> crystallizes in the <em>C</em>2/c space group. The photochromic properties of two compounds were studied under ambient conditions. Upon UV irradiation, compound <strong>1</strong> exhibits a rapid and reversible color change. Compound <strong>2</strong>, however, shows no noticeable photochromic response under similar conditions. Structural analysis indicates that strong hydrogen bonding in compound <strong>1</strong> contribute to its chromic stability and reversible electron transfer between electron-donating and electron-withdrawing groups. These findings highlight the importance of metal coordination environments and noncovalent interactions in the design of advanced viologen-based photochromic materials.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122648"},"PeriodicalIF":2.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611691","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}
引用次数: 0
Nickel complexes of NHC and phosphorus ligands in catalyzing CH bond functionalization reactions
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-11 DOI: 10.1016/j.ica.2025.122646
Shakir Irfan Sisodia , Radhika Malav , Sriparna Ray
{"title":"Nickel complexes of NHC and phosphorus ligands in catalyzing CH bond functionalization reactions","authors":"Shakir Irfan Sisodia ,&nbsp;Radhika Malav ,&nbsp;Sriparna Ray","doi":"10.1016/j.ica.2025.122646","DOIUrl":"10.1016/j.ica.2025.122646","url":null,"abstract":"<div><div>Organometallic catalysts have made serious inroads to achieve a number of synthetically valuable organic reactions that would otherwise seem impossible to materialize. Despite the enormous success of 4d and 5d metals (e.g., Ir, Pd, Rh) in various catalytic systems in the last several decades, they have made partial headway into this field due to their scarcity and cost-ineffectiveness. To overcome these obstacles, complexes containing relatively abundant, affordable, and more environmentally benign 3d metals, such as iron, nickel, and cobalt are being explored for utility in different organic transformations. Recently various research groups have investigated the prospects of these transition metals in catalyzing the C<img>H bond functionalization reactions. Such reactions enable the synthesis of various biologically active compounds, including the naturally occurring compounds, pharmaceutical drug molecules and agriculturally essential products. These base metals provide a new technique for the formation of C<img>X bonds (X = Carbon or heteroatom) in an extremely controlled and selective way without the requirement of pre-functionalization. This review discusses the detailed synthetic procedures of nickel-catalyzed functionalization of inert C<img>H bonds, in presence of N-heterocyclic carbene ligands and phosphorus-based ligands, thereby forming important organic synthons containing different C<img>X bonds (X = Carbon or heteroatom).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122646"},"PeriodicalIF":2.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620631","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}
引用次数: 0
Au(I) complexes bearing allyldiphenylphosphine and thiolate ligands: Synthesis, structural characterization, and biological evaluation
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-11 DOI: 10.1016/j.ica.2025.122647
Mahsa Zare , Hasti Ahmadi Mirsadeghi , Zahra Shamsi , Masood Fereidoonnezhad , Hamid R. Shahsavari
{"title":"Au(I) complexes bearing allyldiphenylphosphine and thiolate ligands: Synthesis, structural characterization, and biological evaluation","authors":"Mahsa Zare ,&nbsp;Hasti Ahmadi Mirsadeghi ,&nbsp;Zahra Shamsi ,&nbsp;Masood Fereidoonnezhad ,&nbsp;Hamid R. Shahsavari","doi":"10.1016/j.ica.2025.122647","DOIUrl":"10.1016/j.ica.2025.122647","url":null,"abstract":"<div><div>This study presents the synthesis of gold(I) thiolate complexes, [Au(SR)(PPh<sub>2</sub>allyl)], PPh<sub>2</sub>allyl refers to allyldiphenylphosphine, and SR represents the deprotonated forms of various thiols, including pyridine-2-thiol (HSpy, <strong>1a</strong>), pyrimidine-2-thiol (HSpyN, <strong>1b</strong>), benzothiazole-2-thiol (HSbt, <strong>1c</strong>), and benzimidazole-2-thiol (Sbi, <strong>1d</strong>). The complexes were prepared via nucleophilic substitution reactions between chlorogold complex [AuCl(PPh<sub>2</sub>allyl)], <strong>A</strong>, and in situ generated thiolate salts under inert conditions. Characterization was performed using NMR spectroscopy and HR ESI-Mass, while single-crystal X-ray diffraction provided structural confirmation for <strong>A</strong> and <strong>1b</strong>. The anticancer activity of these gold complexes was assessed in three human cancer cell lines: lung (A549), ovarian (SKOV3), and breast (MCF-7), alongside a non-cancerous breast cell line (MCF-10 A). The results revealed promising antitumor effects, with <strong>1a</strong> and <strong>1b</strong> demonstrating superior selectivity and potency compared to standard treatments such as cisplatin and auranofin. These compounds demonstrated a good selectivity index. Further investigations indicated that <strong>1b</strong> induces 77.0 % apoptosis in a dose-dependent manner, suggesting its potential as a therapeutic agent. Additionally, <strong>1b</strong>'s effects on cell cycle progression were observed, with higher concentrations promoting S phase entry, which may influence cell viability. Although genotoxicity was noted, the primary mechanism of action for <strong>1b</strong> appears to be the induction of apoptosis rather than direct DNA interaction. Correlating cytotoxicity data with molecular docking results revealed a trend where compounds with stronger binding affinities to DNA and thioredoxin reductase (TrxR), particularly <strong>1b</strong> and <strong>1d</strong>, exhibited lower IC<sub>50</sub> values. Mechanistic insights were refined by acknowledging the dynamic reactivity of these complexes with TrxR's selenocysteine, suggesting that docking results represent initial binding prior to potential ligand exchange. Although some genotoxicity was observed, the primary mechanism appears to be TrxR-mediated apoptosis rather than direct DNA targeting, consistent with broader literature emphasizing protein interactions over nucleic acid effects. These findings underscore the therapeutic potential of these gold complexes in targeting cancer cells, highlighting their promise as selective anticancer agents.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122647"},"PeriodicalIF":2.7,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143620551","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}
引用次数: 0
Preparation and properties of a series of discrete zinc-rare earth heterometallic complexes based on 2,4-dichlorobenzoate and 2,2′-bipyridine
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-10 DOI: 10.1016/j.ica.2025.122644
Shu-Fang Zheng , Jin-Sheng Zhang , Zhen-Yu Yang, Dong-Mei Ren, Bin-Qiu Liu, Ju-Wen Zhang
{"title":"Preparation and properties of a series of discrete zinc-rare earth heterometallic complexes based on 2,4-dichlorobenzoate and 2,2′-bipyridine","authors":"Shu-Fang Zheng ,&nbsp;Jin-Sheng Zhang ,&nbsp;Zhen-Yu Yang,&nbsp;Dong-Mei Ren,&nbsp;Bin-Qiu Liu,&nbsp;Ju-Wen Zhang","doi":"10.1016/j.ica.2025.122644","DOIUrl":"10.1016/j.ica.2025.122644","url":null,"abstract":"<div><div>By using 2,4-dichlorobenzoic acid (2,4-HDCB) and 2,2′-bipyridine (2,2′-bpy) as mixed ligands, a series of Zn(II)-Ln(III) heterometallic complexes were successfully prepared by solvothermal method, namely [Ln<sub>2</sub>Zn<sub>2</sub>(2,4-DCB)<sub>10</sub>(2,2′-bpy)<sub>2</sub>] [Ln = Nd (<strong>1</strong>), Sm (<strong>2</strong>), Eu (<strong>3</strong>), Gd (<strong>4</strong>), Tb (<strong>5</strong>), Dy (<strong>6</strong>), Er (<strong>7</strong>) and Yb (<strong>8</strong>)]. Complexes <strong>1</strong>–<strong>8</strong> were characterized by single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), elemental analysis (EA), Fourier transform infrared (FT-IR) spectroscopy as well as thermogravimetric analysis (TGA) and differential thermoanalysis (DTA). These eight complexes are isomorphic. They possess discrete linear tetranuclear cluster structures formed by the 2,4-DCB anions bridging the Zn(II) and Ln(III) ions. The adjacent tetranuclear clusters can be connected through the π–π interactions into a two-dimensional (2D) supramolecular layer. The photoluminescent properties of <strong>2</strong>, <strong>3</strong>, <strong>5</strong> and <strong>6</strong> as well as the magnetic properties of <strong>1</strong> and <strong>4</strong>–<strong>8</strong> were investigated in detail. The characteristic luminescences of Ln(III) for <strong>2</strong>, <strong>3</strong>, <strong>5</strong> and <strong>6</strong> as well as the ferromagnetic couplings between the Ln(III) ions for <strong>4</strong>–<strong>7</strong> were observed. Complex <strong>6</strong> exhibits a slow magnetic relaxation behavior.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122644"},"PeriodicalIF":2.7,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611690","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}
引用次数: 0
Photoluminescent Pt(II) and Pd(II) complexes [M(diphosphine)(btdt)] of the 2,1,3-benzothiadiazole-5,6-dithiolate ligand
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-09 DOI: 10.1016/j.ica.2025.122636
P.A. Martynenko, D.A. Bashirov, T.S. Sukhikh, S.N. Konchenko
{"title":"Photoluminescent Pt(II) and Pd(II) complexes [M(diphosphine)(btdt)] of the 2,1,3-benzothiadiazole-5,6-dithiolate ligand","authors":"P.A. Martynenko,&nbsp;D.A. Bashirov,&nbsp;T.S. Sukhikh,&nbsp;S.N. Konchenko","doi":"10.1016/j.ica.2025.122636","DOIUrl":"10.1016/j.ica.2025.122636","url":null,"abstract":"<div><div>We study luminescent properties of complexes with 2,1,3-benzothiadiazole-5,6-dithiolate (btdt<sup>2−</sup>) that combines chromophore heterocyclic unit and chelating thiolate groups. A series of new heteroligand complexes with the general formula [M(dppx)(btdt)] were chosen (M = Pt, Pd; dppx = diphenylphosphinomethane (dppm), diphenylphosphinoethane (dppe) and diphenylphosphinoethilene (dppen). Combined experimental and TD-DFT studies reveal negligible effect of the diphosphine ligands on the absorption spectra of the complexes in the solid state and solutions. The first non-dark absorption band at 410–430 nm is attributed to an intraligand (localized on btdt moiety) transition with a minor contribution of a metal–to–ligand charge transfer. In solid state, all complexes exhibit vibrationally-resolved phosphorescence at room temperature in the range of 650–800 nm with a large Stokes shift of ca. 8800 cm<sup>−1</sup>, and with the observed lifetimes of the excited state of 5–110 μs. The presence of an emission signal for [Pd(dppx)(btdt)] is a rare case of room-temperature phosphorescent Pd complexes. In the THF solutions under an argon atmosphere, only the Pt complexes reveal luminescent signal peaked at 650–800 nm, which is quenched upon contact with air.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122636"},"PeriodicalIF":2.7,"publicationDate":"2025-03-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143592158","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}
引用次数: 0
Self-assembled palladium(II) metallacycles bearing imidazole motifs: Synthesis, characterization, and their in vitro cytotoxicity evaluation
IF 2.7 3区 化学
Inorganica Chimica Acta Pub Date : 2025-03-08 DOI: 10.1016/j.ica.2025.122638
Saurabh Kumar , Kanisha Kar , Mukesh Kumar Singh , Arpita Chandra , Neeladri Das
{"title":"Self-assembled palladium(II) metallacycles bearing imidazole motifs: Synthesis, characterization, and their in vitro cytotoxicity evaluation","authors":"Saurabh Kumar ,&nbsp;Kanisha Kar ,&nbsp;Mukesh Kumar Singh ,&nbsp;Arpita Chandra ,&nbsp;Neeladri Das","doi":"10.1016/j.ica.2025.122638","DOIUrl":"10.1016/j.ica.2025.122638","url":null,"abstract":"<div><div>Four unique highly charged palladacycles (<strong>Pd1</strong>–<strong>Pd4</strong>) were synthesized in high yield using a linear and rotationally flexible diimidazole donor tecton 4,4′-di(1<em>H</em>-imidazol-1-yl)-1,1′-biphenyl (<strong>L1</strong>) in combination with <em>cis</em>-blocked [Pd(en)(NO<sub>3</sub>)<sub>2</sub>] acceptor and various other rigid pyridyl donors. A combination of NMR (<sup>1</sup>H NMR and <sup>1</sup>H–DOSY), mass spectrometry (MS), and density functional theory (DFT) calculations were used to characterize the metallacycles. Theoretical studies revealed the presence of adequate cavity dimensions in the palladacycles. Literature reviews have shown that strongly coordinating or chelating ligands can stabilize palladium ions, reducing their physiological reactivity while enhancing their anticancer properties. Palladium(II) complexes are reported to exhibit significant cytotoxic effects towards triple negative breast cancer cell line MDA-MB-231. In light of this, the cytotoxicity of synthesized palladacycles (<strong>Pd1</strong>–<strong>Pd4</strong>) was examined. The data revealed that palladacycles (<strong>Pd1</strong>-<strong>Pd4</strong>) exhibited selective cytotoxicity, effectively targeting human triple-negative breast cancer cells (MDA-MB-231) while remaining nontoxic at the same inhibitory concentration (IC<sub>50</sub>) to healthy human embryonic kidney cells (HEK-293). This study shows the utility of <strong>Pd1</strong>–<strong>Pd4</strong> as potential cytotoxic agents. Further, this research opens new avenues for advanced research and clinical trials in the foreseeable future.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"581 ","pages":"Article 122638"},"PeriodicalIF":2.7,"publicationDate":"2025-03-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143611663","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}
引用次数: 0
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