Pub Date : 2026-01-26Epub Date: 2025-10-30DOI: 10.1016/j.ica.2025.122980
R. Divya Mohan, S. Sarukrishna, Aparna Surendra Babu, Dhaya Santhosh, S. Ahsana Fathima, B. Parvathy
Transition metals are known for their significant biological relevance, which is often enhanced upon coordination with Schiff-base ligands. Schiff bases, typically synthesized via the condensation of primary amines with aldehydes or ketones, form stable complexes exhibiting a range of biological properties. These include antifungal, antiviral, antitumor, anti-inflammatory, and cytotoxic activities, positioning them as promising candidates in medicinal chemistry. Moreover, their applications in homogeneous and heterogeneous catalysis have garnered increasing attention in recent years. Among various metal complexes, Copper(II) Schiff base complexes have demonstrated particularly strong bioactivity, notably as antimicrobial agents and antioxidants. This review highlights the synthesis and biological evaluation of copper(II) Schiff base complexes, structured based on the denticity of the coordinating ligands with a focused discussion on their antioxidant properties. The study encompasses original articles and review papers on the antioxidant activity of Cu(II) Schiff base complexes reported from 2010 to 2023, with selected relevant reports from 2006 also included.
{"title":"A review of ligand denticity in copper–Schiff Base complexes: Structural tuning toward enhanced antioxidant activity","authors":"R. Divya Mohan, S. Sarukrishna, Aparna Surendra Babu, Dhaya Santhosh, S. Ahsana Fathima, B. Parvathy","doi":"10.1016/j.ica.2025.122980","DOIUrl":"10.1016/j.ica.2025.122980","url":null,"abstract":"<div><div>Transition metals are known for their significant biological relevance, which is often enhanced upon coordination with Schiff-base ligands. Schiff bases, typically synthesized via the condensation of primary amines with aldehydes or ketones, form stable complexes exhibiting a range of biological properties. These include antifungal, antiviral, antitumor, anti-inflammatory, and cytotoxic activities, positioning them as promising candidates in medicinal chemistry. Moreover, their applications in homogeneous and heterogeneous catalysis have garnered increasing attention in recent years. Among various metal complexes, Copper(II) Schiff base complexes have demonstrated particularly strong bioactivity, notably as antimicrobial agents and antioxidants. This review highlights the synthesis and biological evaluation of copper(II) Schiff base complexes, structured based on the denticity of the coordinating ligands with a focused discussion on their antioxidant properties. The study encompasses original articles and review papers on the antioxidant activity of Cu(II) Schiff base complexes reported from 2010 to 2023, with selected relevant reports from 2006 also included.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122980"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145419055","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}
Two novel holmium mercury isonicotinic acid/nicotinic acid materials, [Ho(HIA)3(H2O)2]2n·3n(HgBr4)·4nH2O (1) (HIA = isonicotinic acid) and [Ho(HNA)3(H2O)2]2n·3n(HgCl4)·4nH2O (2) (HNA = nicotinic acid), were obtained through hydrothermal reactions, and their structural features were analyzed by single – crystal X – ray diffraction. Both of these complexes display a one – dimensional (1 – D) chain – like framework. The lanthanide ions within them are in eight – coordination configurations, and the mercury ions are in four – coordination patterns. Semiconductor bandgaps were ascertained from solid-state UV/Vis diffuse reflectance measurements, yielding values of 3.21 eV for complex 1 and 2.98 eV for complex 2. Solid-state sample-based photoluminescence investigations indicate that both complexes produce green upconverting photoluminescence. The underlying cause of this photoluminescence is the characteristic emission due to the 4f electron intrashell transition (5S2 → 5I8) in Ho3+ ions existing in both complexes. The Commission Internationale de l'Éclairage (CIE) color space positions compounds 1 and 2 at (0.6679, 0.3318) and (0.2446, 0.7376), with associated correlated color temperatures measured as 6497 K and 6814 K.
{"title":"Preparation, crystal structures and photophysical properties of two green upconversion photoluminescence holmium mercury complexes","authors":"Hao-Dong Liu, Long-Hua Zeng, Xi-Yu Shao, Cheng Liu, Wen-Tong Chen","doi":"10.1016/j.ica.2025.122975","DOIUrl":"10.1016/j.ica.2025.122975","url":null,"abstract":"<div><div>Two novel holmium mercury isonicotinic acid/nicotinic acid materials, [Ho(HIA)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>2<em>n</em></sub>·3<em>n</em>(HgBr<sub>4</sub>)·4<em>n</em>H<sub>2</sub>O (<strong>1</strong>) (HIA = isonicotinic acid) and [Ho(HNA)<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>]<sub>2<em>n</em></sub>·3<em>n</em>(HgCl<sub>4</sub>)·4<em>n</em>H<sub>2</sub>O (<strong>2</strong>) (HNA = nicotinic acid), were obtained through hydrothermal reactions, and their structural features were analyzed by single – crystal X – ray diffraction. Both of these complexes display a one – dimensional (1 – D) chain – like framework. The lanthanide ions within them are in eight – coordination configurations, and the mercury ions are in four – coordination patterns. Semiconductor bandgaps were ascertained from solid-state UV/Vis diffuse reflectance measurements, yielding values of 3.21 eV for complex <strong>1</strong> and 2.98 eV for complex <strong>2</strong>. Solid-state sample-based photoluminescence investigations indicate that both complexes produce green upconverting photoluminescence. The underlying cause of this photoluminescence is the characteristic emission due to the 4f electron intrashell transition (<sup>5</sup><em>S</em><sub>2</sub> → <sup>5</sup><em>I</em><sub>8</sub>) in Ho<sup>3+</sup> ions existing in both complexes. The Commission Internationale de l'Éclairage (CIE) color space positions compounds <strong>1</strong> and <strong>2</strong> at (0.6679, 0.3318) and (0.2446, 0.7376), with associated correlated color temperatures measured as 6497 K and 6814 K.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122975"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145525956","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-10-17DOI: 10.1016/j.ica.2025.122954
Md. Sohag Hasan , Md. Nazmul Huda , Subas Rajbangshi , Vladimir N. Nesterov , Shariff E. Kabir , Shishir Ghosh
The reactions of two diphosphines namely 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(diphenylphosphino)benzene (dppbz) with saccharinate-bridged triosmium cluster [Os3(CO)10(μ-H)(μ-sac)] (1) have been investigated. Thus, the reaction of 1 with dppe leads to the formation of triosmium [Os3(CO)8(κ2-dppe)(μ-H)(μ-sac)] (2), in which the dppe ligand chelates an osmium center, as the major product together with hexaosmium [{Os3(CO)9(μ-H)(μ-sac)}2(κ2-dppe)] (3), in which the dppe ligand acts as a linker between two triosmium units, in minor amount. In contrast, a similar reaction between 1 and dppbz affords two triosmium clusters [Os3(CO)8(κ2-dppbz)(μ-H)(μ-sac)] (4) and [Os3(CO)9(κ2-dppbz)(μ-H){κ1(N)-sac}] (5), respectively, both of which contain a chelating dppbz ligand. However, the sac ligand bridges an osmium-osmium edge in 4, whereas it is coordinated to a single osmium using the nitrogen in 5. Control experiments show that 5 converts into 4via decarbonylation under similar experimental conditions. Cluster 4 reacts with triphenylphosphine (PPh3) to furnish three triosmium clusters; the simple phosphine-substituted [Os3(CO)7(κ2-dppbz)(μ-H)(PPh3)(μ-sac)] (6) and the isomeric [Os3(CO)6(κ2-dppbz)(μ-H)2(μ-η1,κ1-PPh2C6H4)(μ-sac)] (7) and [Os3(CO)6(κ2-dppbz)(μ-H)2(μ-η1,κ1-PPh2C6H4)(μ-sac)] (8) formed through ortho-metalation of one of the phenyl groups of the coordinated PPh3 ligand. Cluster 6 is the precursor of 8 since the former converts in to the latter upon heating. All the products have been characterized by analytical and spectroscopic data, and their molecular structures have been determined by single crystal X-ray diffraction analysis. Cluster 5 exists in four isomeric forms in solution at room temperature, and its fluxional behavior has been probed by VT NMR experiments.
{"title":"Tri and hexaosmium clusters containing saccharinate and diphosphine ligands: Synthesis, crystal structure, fluxional behavior and reactivity","authors":"Md. Sohag Hasan , Md. Nazmul Huda , Subas Rajbangshi , Vladimir N. Nesterov , Shariff E. Kabir , Shishir Ghosh","doi":"10.1016/j.ica.2025.122954","DOIUrl":"10.1016/j.ica.2025.122954","url":null,"abstract":"<div><div>The reactions of two diphosphines namely 1,2-bis(diphenylphosphino)ethane (dppe) and 1,2-bis(diphenylphosphino)benzene (dppbz) with saccharinate-bridged triosmium cluster [Os<sub>3</sub>(CO)<sub>10</sub>(μ-H)(μ-sac)] (<strong>1</strong>) have been investigated. Thus, the reaction of <strong>1</strong> with dppe leads to the formation of triosmium [Os<sub>3</sub>(CO)<sub>8</sub>(κ<sup>2</sup>-dppe)(μ-H)(μ-sac)] (<strong>2</strong>), in which the dppe ligand chelates an osmium center, as the major product together with hexaosmium [{Os<sub>3</sub>(CO)<sub>9</sub>(μ-H)(μ-sac)}<sub>2</sub>(κ<sup>2</sup>-dppe)] (<strong>3</strong>), in which the dppe ligand acts as a linker between two triosmium units, in minor amount. In contrast, a similar reaction between <strong>1</strong> and dppbz affords two triosmium clusters [Os<sub>3</sub>(CO)<sub>8</sub>(κ<sup>2</sup>-dppbz)(μ-H)(μ-sac)] (<strong>4</strong>) and [Os<sub>3</sub>(CO)<sub>9</sub>(κ<sup>2</sup>-dppbz)(μ-H){κ<sup>1</sup>(N)-sac}] (<strong>5</strong>), respectively, both of which contain a chelating dppbz ligand. However, the sac ligand bridges an osmium-osmium edge in <strong>4</strong>, whereas it is coordinated to a single osmium using the nitrogen in <strong>5</strong>. Control experiments show that <strong>5</strong> converts into <strong>4</strong> <em>via</em> decarbonylation under similar experimental conditions. Cluster <strong>4</strong> reacts with triphenylphosphine (PPh<sub>3</sub>) to furnish three triosmium clusters; the simple phosphine-substituted [Os<sub>3</sub>(CO)<sub>7</sub>(κ<sup>2</sup>-dppbz)(μ-H)(PPh<sub>3</sub>)(μ-sac)] (<strong>6</strong>) and the isomeric [Os<sub>3</sub>(CO)<sub>6</sub>(κ<sup>2</sup>-dppbz)(μ-H)<sub>2</sub>(μ-η<sup>1</sup>,κ<sup>1</sup>-PPh<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)(μ-sac)] (<strong>7</strong>) and [Os<sub>3</sub>(CO)<sub>6</sub>(κ<sup>2</sup>-dppbz)(μ-H)<sub>2</sub>(μ-η<sup>1</sup>,κ<sup>1</sup>-PPh<sub>2</sub>C<sub>6</sub>H<sub>4</sub>)(μ-sac)] (<strong>8</strong>) formed through <em>ortho</em>-metalation of one of the phenyl groups of the coordinated PPh<sub>3</sub> ligand. Cluster <strong>6</strong> is the precursor of <strong>8</strong> since the former converts in to the latter upon heating. All the products have been characterized by analytical and spectroscopic data, and their molecular structures have been determined by single crystal X-ray diffraction analysis. Cluster <strong>5</strong> exists in four isomeric forms in solution at room temperature, and its fluxional behavior has been probed by VT NMR experiments.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122954"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145335184","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-11-04DOI: 10.1016/j.ica.2025.122986
Pengxiao Guo , Rongqi Wang , Yadong Zhou , Chaochuang Yin , Yizhu Lei , Yinyan Wang , Kang Chen , Li Sun , Ziao Zong , Hu Wang
Herein, we explore the development of three copper(II) Schiff base complexes (Cu-SBC, C1-C3) aimed at inhibiting urease (UA), achieved through the thoughtful design of ligands. By integrating a fluorinated Schiff base ligand (SBL) with auxiliary ligands—namely, 2-methylimidazole, 2-ethylimidazole, and 6,6′-dimethyl-2,2′-bipyridine—this research systematically examines the impact of steric factors on the inhibition of the UA enzyme. The synthesized complexes underwent comprehensive characterization, including crystallographic analysis. The three synthesized Cu(II) complexes exhibit two distinct coordination geometries dictated by their auxiliary ligands. C1 and C2 display four-coordinate distorted square planar geometries, while C3 adopts a five-coordinate distorted square pyramidal configuration. The biological evaluation revealed that C1 demonstrated a markedly enhanced UA inhibitory activity compared to the standard reference acetohydroxamic acid (IC50: 6.12 ± 0.44 vs. 27.73 ± 2.93 μM). Computational methodologies were employed to complement the experimental investigations, elucidating the molecular underpinnings of the observed activity disparities among the complexes. Consequently, the structure-activity relationship analysis indicates that steric hindrance is crucial in modulating the UA inhibitory activity, providing important perspectives for the development of new UA inhibitors and their potential uses in biomedicine.
{"title":"A multifaceted study of three Cu(II) Schiff base complexes as urease inhibitors: Derived from experimental and computational approaches","authors":"Pengxiao Guo , Rongqi Wang , Yadong Zhou , Chaochuang Yin , Yizhu Lei , Yinyan Wang , Kang Chen , Li Sun , Ziao Zong , Hu Wang","doi":"10.1016/j.ica.2025.122986","DOIUrl":"10.1016/j.ica.2025.122986","url":null,"abstract":"<div><div>Herein, we explore the development of three copper(II) Schiff base complexes (Cu-SBC, <strong>C1</strong>-<strong>C3</strong>) aimed at inhibiting urease (UA), achieved through the thoughtful design of ligands. By integrating a fluorinated Schiff base ligand (SBL) with auxiliary ligands—namely, 2-methylimidazole, 2-ethylimidazole, and 6,6′-dimethyl-2,2′-bipyridine—this research systematically examines the impact of steric factors on the inhibition of the UA enzyme. The synthesized complexes underwent comprehensive characterization, including crystallographic analysis. The three synthesized Cu(II) complexes exhibit two distinct coordination geometries dictated by their auxiliary ligands. <strong>C1</strong> and <strong>C2</strong> display four-coordinate distorted square planar geometries, while <strong>C3</strong> adopts a five-coordinate distorted square pyramidal configuration. The biological evaluation revealed that <strong>C1</strong> demonstrated a markedly enhanced UA inhibitory activity compared to the standard reference acetohydroxamic acid (IC<sub>50</sub>: 6.12 ± 0.44 vs. 27.73 ± 2.93 μM). Computational methodologies were employed to complement the experimental investigations, elucidating the molecular underpinnings of the observed activity disparities among the complexes. Consequently, the structure-activity relationship analysis indicates that steric hindrance is crucial in modulating the UA inhibitory activity, providing important perspectives for the development of new UA inhibitors and their potential uses in biomedicine.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122986"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145525955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-10-25DOI: 10.1016/j.ica.2025.122962
Daniil A. Bardonov , Svetlana S. Degtyareva , Konstantin A. Lyssenko , Ilya E. Nifant'ev , Mikhail E. Minyaev , Dmitrii M. Roitershtein
A series of tris(triphenylcyclopentadienyl) ate-complexes [CpPh33LnCl]−[MLn]+ (Ln = La, Ce, Pr) MLn = Li(THF)4 (Ln1), K(18-crown-6)(THF) (Ln2), Na(THF)6 (La3) were synthesized by the straightforward salt-metathesis method. All the structural types have been studied by single-crystal X-ray diffraction. The formation of complexes results from the concerted arrangement of the phenyl substituents of the three bulky triphenylcyclopentadienyl ligands respect to each other. Synthesis of tris(triphenylcyclopentadienyl) complexes of lanthanides with an ionic radius less than that of praseodymium could not be achieved. In conditions unfavorable for formation of the ate-complex, only La3, can be obtained, cerium reaction results in an inseparable mixture of compounds, while praseodymium yields the bis(cyclopentadienyl) complex [CpPh32PrCl(THF)] (Pr4).
{"title":"Tris(triphenylcyclopentadienyl) lanthanide complexes – at the edge of steric overcrowding","authors":"Daniil A. Bardonov , Svetlana S. Degtyareva , Konstantin A. Lyssenko , Ilya E. Nifant'ev , Mikhail E. Minyaev , Dmitrii M. Roitershtein","doi":"10.1016/j.ica.2025.122962","DOIUrl":"10.1016/j.ica.2025.122962","url":null,"abstract":"<div><div>A series of tris(triphenylcyclopentadienyl) ate-complexes [Cp<sup>Ph3</sup><sub>3</sub>LnCl]<sup>−</sup>[ML<sub>n</sub>]<sup>+</sup> (Ln = La, Ce, Pr) ML<sub>n</sub> = Li(THF)<sub>4</sub> (<strong>Ln1</strong>), K(18-crown-6)(THF) (<strong>Ln2</strong>), Na(THF)<sub>6</sub> (<strong>La3</strong>) were synthesized by the straightforward salt-metathesis method. All the structural types have been studied by single-crystal X-ray diffraction. The formation of complexes results from the concerted arrangement of the phenyl substituents of the three bulky triphenylcyclopentadienyl ligands respect to each other. Synthesis of tris(triphenylcyclopentadienyl) complexes of lanthanides with an ionic radius less than that of praseodymium could not be achieved. In conditions unfavorable for formation of the ate-complex, only <strong>La3</strong>, can be obtained, cerium reaction results in an inseparable mixture of compounds, while praseodymium yields the bis(cyclopentadienyl) complex [Cp<sup>Ph3</sup><sub>2</sub>PrCl(THF)] (<strong>Pr4</strong>).</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122962"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145419057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-11-04DOI: 10.1016/j.ica.2025.122984
Hadi Kargar , Maciej Kubicki , Mehdi Fallah-Mehrjardi , Hamid Reza Zare-Mehrjardi , Fatemeh Abyar , Khurram Shahzad Munawar , Muhammad Ashfaq
A series of nitro-substituted salophen Schiff base complexes, NiL, CuL, and ZnL, were synthesized and characterized using elemental analysis and various spectroscopic techniques. Single-crystal X-ray diffraction of NiL confirmed tetradentate coordination of the ligand to the nickel center, forming a slightly distorted square planar geometry stabilized by extensive intermolecular interactions such as CH⋯O, π⋯π, π⋯Ni, CH⋯π, and NO⋯π, as revealed by Hirshfeld surface analysis. Cyclic voltammetry measurements demonstrated quasi-reversible redox behavior for Ni(II), Cu(II), and Zn(II) complexes, with the Cu(II)/Cu(I) process being the most prominent under physiological pH conditions. Density functional theory (DFT) calculations supported the experimental observations, indicating a smaller HOMO–LUMO energy gap for the synthesized complexes, consistent with their enhanced redox activity. Molecular electrostatic potential (MEP) and natural bond orbital (NBO) analyses revealed significant charge delocalization and strong donor–acceptor interactions, highlighting the mixed ionic–covalent nature of metal–ligand bonding. Overall, experimental and theoretical findings collectively establish the structure–property relationships and electronic characteristics of these nitro-substituted salophen Schiff base complexes.
{"title":"Synthesis, characterization, electrochemical, and theoretical investigation of nitro-substituted salophen Schiff base complexes","authors":"Hadi Kargar , Maciej Kubicki , Mehdi Fallah-Mehrjardi , Hamid Reza Zare-Mehrjardi , Fatemeh Abyar , Khurram Shahzad Munawar , Muhammad Ashfaq","doi":"10.1016/j.ica.2025.122984","DOIUrl":"10.1016/j.ica.2025.122984","url":null,"abstract":"<div><div>A series of nitro-substituted salophen Schiff base complexes, <strong>NiL</strong>, <strong>CuL</strong>, and <strong>ZnL</strong>, were synthesized and characterized using elemental analysis and various spectroscopic techniques. Single-crystal X-ray diffraction of <strong>NiL</strong> confirmed tetradentate coordination of the ligand to the nickel center, forming a slightly distorted square planar geometry stabilized by extensive intermolecular interactions such as C<img>H⋯O, π⋯π, π⋯Ni, C<img>H⋯π, and N<img>O⋯π, as revealed by Hirshfeld surface analysis. Cyclic voltammetry measurements demonstrated quasi-reversible redox behavior for Ni(II), Cu(II), and Zn(II) complexes, with the Cu(II)/Cu(I) process being the most prominent under physiological pH conditions. Density functional theory (DFT) calculations supported the experimental observations, indicating a smaller HOMO–LUMO energy gap for the synthesized complexes, consistent with their enhanced redox activity. Molecular electrostatic potential (MEP) and natural bond orbital (NBO) analyses revealed significant charge delocalization and strong donor–acceptor interactions, highlighting the mixed ionic–covalent nature of metal–ligand bonding. Overall, experimental and theoretical findings collectively establish the structure–property relationships and electronic characteristics of these nitro-substituted salophen Schiff base complexes.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122984"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463709","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-10-28DOI: 10.1016/j.ica.2025.122979
Fatemeh Ghasemi , Khaled Ghasemi
This systematic review comprehensively charts five decades of advances in the synthesis, structure, and properties of nickel(II) complexes with 2,6-pyridinedicarboxylic acid (dipicolinic acid, H₂dipic). Unlike previous reports, this work critically analyzes exclusively crystallographically characterized examples, categorizing them based on nuclearity—from mononuclear and binuclear to higher nuclearity clusters (trinuclear, tetranuclear) and coordination polymers—and ligand protonation state (H₂dipic, Hdipic−, dipic2−). The analysis reveals how the consistent κ3-O,N,O′ coordination mode of the dipicolinate ligand provides a robust platform for engineering functionality through strategic selection of ancillary ligands and synthetic conditions. The review dedicates significant focus to establishing structure-property relationships, providing a detailed discussion of magnetic characteristics—from single-ion magnetism and supramolecular exchange to strong coupling in radical-bridged systems—alongside emerging applications in catalysis, biomedicine, and materials science. By compiling and critically evaluating all available X-ray structures, this work not only serves as a definitive reference but also identifies overarching trends and design principles, such as the “Metal Affinity Rule” for heterometallic assembly and the role of kinetic versus thermodynamic control in directing structural outcomes. This review underscores the evolution of nickel-dipicolinate chemistry from serendipitous discovery to rational design, highlighting its significant contributions to coordination chemistry and providing a roadmap for future research.
{"title":"Fifty years of advances in the synthesis, structure, and properties of nickel-Dipicolinate complexes: A systematic review","authors":"Fatemeh Ghasemi , Khaled Ghasemi","doi":"10.1016/j.ica.2025.122979","DOIUrl":"10.1016/j.ica.2025.122979","url":null,"abstract":"<div><div>This systematic review comprehensively charts five decades of advances in the synthesis, structure, and properties of nickel(II) complexes with 2,6-pyridinedicarboxylic acid (dipicolinic acid, H₂dipic). Unlike previous reports, this work critically analyzes exclusively crystallographically characterized examples, categorizing them based on nuclearity—from mononuclear and binuclear to higher nuclearity clusters (trinuclear, tetranuclear) and coordination polymers—and ligand protonation state (H₂dipic, Hdipic<sup>−</sup>, dipic<sup>2−</sup>). The analysis reveals how the consistent κ<sup>3</sup>-O,N,O′ coordination mode of the dipicolinate ligand provides a robust platform for engineering functionality through strategic selection of ancillary ligands and synthetic conditions. The review dedicates significant focus to establishing structure-property relationships, providing a detailed discussion of magnetic characteristics—from single-ion magnetism and supramolecular exchange to strong coupling in radical-bridged systems—alongside emerging applications in catalysis, biomedicine, and materials science. By compiling and critically evaluating all available X-ray structures, this work not only serves as a definitive reference but also identifies overarching trends and design principles, such as the “Metal Affinity Rule” for heterometallic assembly and the role of kinetic versus thermodynamic control in directing structural outcomes. This review underscores the evolution of nickel-dipicolinate chemistry from serendipitous discovery to rational design, highlighting its significant contributions to coordination chemistry and providing a roadmap for future research.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122979"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463710","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-11-05DOI: 10.1016/j.ica.2025.122987
Anton N. Ostrosablin , Vasily A. Ilichev , Anton F. Rogozhin , Olga V. Kuznetsova , Pavel V. Dorovatovskii , Roman V. Rumyantcev , Georgy K. Fukin , Mikhail N. Bochkarev
Complexes of divalent europium with perfluoro-2-mercaptobenzothiazolate (mbtF) and a set of macrocyclic ligands - 18-dbc-6, 18-crown-6, [2.2]cryptand and [2.2.2]cryptand, were synthesized. Accordingly X-ray data, applying of 18-dbc-6 yields complex 1 with a composition Eu(mbtF)2(18-dbc-6) in which 18-dbc-6 acts as hexadentate ligand and one of mbtF ligands is chelately coordinated, while the other exhibits monodentate coordination via the thiolate sulfur. In complexes with 18-crown-6 and [2.2]cryptand macrocyclic ligands with general formulas Eu(mbtF)2(18-crown-6) (2) and Eu(mbtF)2([2.2]cryptand) (3), respectively, show similar hexadentate coordination of macrocyclic ligands but only monodentate coordination mode of mbtF ligands to europium. Additionally, the molecular structure of complex 3 is stabilized by intramolecular N-H…N interactions of [2.2]cryptand and mbtF ligands. A complex with [2.2.2]cryptand ligand of a composition Eu(mbtF)2([2.2.2]cryptand) (4) does not give crystals, however it reacts with copper(I) iodide yielding a highly luminescent europium diiodide [EuI([2.2.2]cryptand)]I (5) which contains a complex cation [EuI([2.2.2]cryptand)]+ where the macrocyclic ligand exhibits octadentate coordination mode.
{"title":"Synthesis and structures of Eu(II) complexes with anionic perfluoro-2-mercaptobenzothiazolate and macrocyclic ligands","authors":"Anton N. Ostrosablin , Vasily A. Ilichev , Anton F. Rogozhin , Olga V. Kuznetsova , Pavel V. Dorovatovskii , Roman V. Rumyantcev , Georgy K. Fukin , Mikhail N. Bochkarev","doi":"10.1016/j.ica.2025.122987","DOIUrl":"10.1016/j.ica.2025.122987","url":null,"abstract":"<div><div>Complexes of divalent europium with perfluoro-2-mercaptobenzothiazolate (mbt<sup>F</sup>) and a set of macrocyclic ligands - 18-dbc-6, 18-crown-6, [2.2]cryptand and [2.2.2]cryptand, were synthesized. Accordingly X-ray data, applying of 18-dbc-6 yields complex <strong>1</strong> with a composition Eu(mbt<sup>F</sup>)<sub>2</sub>(18-dbc-6) in which 18-dbc-6 acts as hexadentate ligand and one of mbt<sup>F</sup> ligands is chelately coordinated, while the other exhibits monodentate coordination via the thiolate sulfur. In complexes with 18-crown-6 and [2.2]cryptand macrocyclic ligands with general formulas Eu(mbt<sup>F</sup>)<sub>2</sub>(18-crown-6) (<strong>2</strong>) and Eu(mbt<sup>F</sup>)<sub>2</sub>([2.2]cryptand) (<strong>3</strong>), respectively, show similar hexadentate coordination of macrocyclic ligands but only monodentate coordination mode of mbt<sup>F</sup> ligands to europium. Additionally, the molecular structure of complex <strong>3</strong> is stabilized by intramolecular N-H…N interactions of [2.2]cryptand and mbt<sup>F</sup> ligands. A complex with [2.2.2]cryptand ligand of a composition Eu(mbt<sup>F</sup>)<sub>2</sub>([2.2.2]cryptand) (<strong>4</strong>) does not give crystals, however it reacts with copper(I) iodide yielding a highly luminescent europium diiodide [EuI([2.2.2]cryptand)]I (<strong>5</strong>) which contains a complex cation [EuI([2.2.2]cryptand)]<sup>+</sup> where the macrocyclic ligand exhibits octadentate coordination mode.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122987"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-10-28DOI: 10.1016/j.ica.2025.122970
Trofim A. Polikovskiy , Victoria E. Gontcharenko , Anna A. Vorobyova , Igor V. Morozov , Konstantin A. Lyssenko , Ilya V. Taydakov
In this study, we report two novel europium(III) complexes, namely (NO)3[Eu2(NO3)9] (1) and (PhenH2)[Eu(NO3)5] (2). The crystal structure of 1 is comprised of three-dimensional anionic framework formed by [Eu(NO3)6] units connected via bridging nitrate groups and nitrosonium cations NO+ located in the pores of the framework. The crystal structure of 2, along with molecular complex [Eu(NO3)5]2−, contains the double-protonated 1,10-phenanthroline cation (PhenH2)2+, serving as a non-coordinated antenna. Single-crystal X-ray diffraction reveals a dodecahedral (in complex 1) and decahedral (in complex 2) Eu3+ coordination environment formed solely by nitrate ligands. Despite the absence of direct bonding, (PhenH2)2+ efficiently sensitizes Eu3+ emission, indicating energy transfer via a long-range dipole-dipole mechanism. Quantum yields are 0.53 for 1 and 0.60 for 2. The overall quantum yield of 2 is 0.51. This work demonstrates the potential of unlinked chromophores in designing efficient lanthanide emitters with tunable architecture and minimized quenching.
{"title":"First evidence of [Eu(NO3)5] complex with 1,10-phenanthrolinium (PhenH2)2+: effect of unlinked antenna on luminescent properties","authors":"Trofim A. Polikovskiy , Victoria E. Gontcharenko , Anna A. Vorobyova , Igor V. Morozov , Konstantin A. Lyssenko , Ilya V. Taydakov","doi":"10.1016/j.ica.2025.122970","DOIUrl":"10.1016/j.ica.2025.122970","url":null,"abstract":"<div><div>In this study, we report two novel europium(III) complexes, namely (NO)<sub>3</sub>[Eu<sub>2</sub>(NO<sub>3</sub>)<sub>9</sub>] (<strong>1</strong>) and (PhenH<sub>2</sub>)[Eu(NO<sub>3</sub>)<sub>5</sub>] (<strong>2</strong>). The crystal structure of <strong>1</strong> is comprised of three-dimensional anionic framework formed by [Eu(NO<sub>3</sub>)<sub>6</sub>] units connected <em>via</em> bridging nitrate groups and nitrosonium cations NO<sup>+</sup> located in the pores of the framework. The crystal structure of <strong>2</strong>, along with molecular complex [Eu(NO<sub>3</sub>)<sub>5</sub>]<sup>2−</sup>, contains the double-protonated 1,10-phenanthroline cation (PhenH<sub>2</sub>)<sup>2+</sup>, serving as a non-coordinated antenna. Single-crystal X-ray diffraction reveals a dodecahedral (in complex <strong>1</strong>) and decahedral (in complex <strong>2</strong>) Eu<sup>3+</sup> coordination environment formed solely by nitrate ligands. Despite the absence of direct bonding, (PhenH<sub>2</sub>)<sup>2+</sup> efficiently sensitizes Eu<sup>3+</sup> emission, indicating energy transfer <em>via</em> a long-range dipole-dipole mechanism. Quantum yields are 0.53 for <strong>1</strong> and 0.60 for <strong>2</strong>. The overall quantum yield of <strong>2</strong> is 0.51. This work demonstrates the potential of unlinked chromophores in designing efficient lanthanide emitters with tunable architecture and minimized quenching.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122970"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26Epub Date: 2025-10-30DOI: 10.1016/j.ica.2025.122982
Gazal Sabharwal, Khilesh C. Dwivedi, Maravanji S. Balakrishna
A tridentate amide-pyridine-monophosphine ligand, {(o-PPh2)C6H4C(O)N(H)CH2 (C5H4N)} (1), has been employed to synthesize a series of AgI and AuI complexes exhibiting diverse nuclearities, coordination modes, and geometries. Reactions of 1 with AgI and AgOAc furnished 1D coordination polymers, [(AgI{{(o-PPh2)C6H4}C(O)N(H)CH2(C5H4N)})n] (2) and [(AgOAc{{(o-PPh2)C6H4}C(O)N(H)CH2(C5H4)})n] (3), with AgI in distorted tetrahedral environments. Treatment with AgBF4, AgClO4, and AgNO3 yielded cationic, dimeric P,N-coordinated complexes [(Ag)2{{(o-PPh2)C6H4}C(O)N(H)CH2(C5H4N)}2-κ2-P, N](X)2 (X = BF4 (4), X = ClO4 (5), X = NO3 (6)), featuring distorted linear AgI centres. Further reactions with AgOTf, AgPF6, and AgSbF6 afforded P,N,O-coordinated dimeric complexes [(Ag)2{{(o-PPh2)C6H4}C(O)(H)CH2(C5H4N)}2-κ)3-P,N,O](X)2 (X = OTf (7), X = PF6 (8), X = SbF6 (9)). Notably, complex 8 exhibits distortion of the typically symmetrical octahedral geometry of the PF6− counterion, attributed to specific intermolecular interactions with the complex. Neutral dimeric complexes [(AgX)2{{(o-PPh2)C6H4}C(O)N(H)CH2(C5H4N)}2-κ)2-P,N] (X = Cl (10), Br (11)) were also isolated, with AgI in distorted trigonal planar geometries. Finally, reaction of 1 with [AuCl(SMe2)] afforded a monomeric P-coordinated AuI complex [(AuCl){{(o-PPh2)C6H4}C(O)N(H)CH2(C5H4N)}-κ)1-P] (12), featuring a distorted linear geometry. These results highlight the versatile coordination behaviour of ligand 1 towards group 11 metal ions, leading to structurally diverse architectures.
{"title":"Amidophosphine-supported AgI complexes: monomeric, dimeric and polymeric forms with diverse coordination geometries","authors":"Gazal Sabharwal, Khilesh C. Dwivedi, Maravanji S. Balakrishna","doi":"10.1016/j.ica.2025.122982","DOIUrl":"10.1016/j.ica.2025.122982","url":null,"abstract":"<div><div>A tridentate amide-pyridine-monophosphine ligand, {(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>C(<em>O</em>)N(H)CH<sub>2</sub> (C<sub>5</sub>H<sub>4</sub>N)} (<strong>1</strong>), has been employed to synthesize a series of Ag<sup>I</sup> and Au<sup>I</sup> complexes exhibiting diverse nuclearities, coordination modes, and geometries. Reactions of <strong>1</strong> with AgI and AgOAc furnished 1D coordination polymers, [(AgI{{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>}C(<em>O</em>)N(H)CH<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>N)})<sub>n</sub>] (<strong>2</strong>) and [(AgOAc{{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>}C(<em>O</em>)N(H)CH<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>)})<sub>n</sub>] (<strong>3</strong>), with Ag<sup>I</sup> in distorted tetrahedral environments. Treatment with AgBF<sub>4</sub>, AgClO<sub>4</sub>, and AgNO<sub>3</sub> yielded cationic, dimeric P,N-coordinated complexes [(Ag)<sub>2</sub>{{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>}C(<em>O</em>)N(H)CH<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>N)}<sub>2</sub>-κ<sup>2</sup>-<em>P, N</em>](X)<sub>2</sub> (X = BF<sub>4</sub> (<strong>4</strong>), X = ClO<sub>4</sub> (<strong>5</strong>), X = NO<sub>3</sub> (<strong>6</strong>)), featuring distorted linear Ag<sup>I</sup> centres. Further reactions with AgOTf, AgPF<sub>6</sub>, and AgSbF<sub>6</sub> afforded P,N,O-coordinated dimeric complexes [(Ag)<sub>2</sub>{{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>}C(O)(H)CH<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>N)}<sub>2</sub>-κ)<sup>3</sup>-<em>P,N,O</em>](X)<sub>2</sub> (X = OTf (<strong>7</strong>), X = PF<sub>6</sub> (<strong>8</strong>), X = SbF<sub>6</sub> (<strong>9</strong>)). Notably, complex <strong>8</strong> exhibits distortion of the typically symmetrical octahedral geometry of the PF<sub>6</sub><sup>−</sup> counterion, attributed to specific intermolecular interactions with the complex. Neutral dimeric complexes [(AgX)<sub>2</sub>{{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>}C(<em>O</em>)N(H)CH<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>N)}<sub>2</sub>-κ)<sup>2</sup>-<em>P,N</em>] (X = Cl (<strong>10</strong>), Br (<strong>11</strong>)) were also isolated, with Ag<sup>I</sup> in distorted trigonal planar geometries. Finally, reaction of <strong>1</strong> with [AuCl(SMe<sub>2</sub>)] afforded a monomeric P-coordinated Au<sup>I</sup> complex [(AuCl){{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>}C(<em>O</em>)N(H)CH<sub>2</sub>(C<sub>5</sub>H<sub>4</sub>N)}-κ)<sup>1</sup>-<em>P</em>] (<strong>12</strong>), featuring a distorted linear geometry. These results highlight the versatile coordination behaviour of ligand <strong>1</strong> towards group 11 metal ions, leading to structurally diverse architectures.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122982"},"PeriodicalIF":3.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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