Pub Date : 2025-10-21DOI: 10.1016/j.ica.2025.122961
Daqing Chen, Chenghui Han
Two isomeric cyclometalated iridium(III) N-heterocyclic carbene (NHC) complexes (1 and 2) bearing a salen ligand were synthesized by treating the [IrIII-salen-(Cl)(CO)] precursor with 1-phenyl-3-methylimidazol-2-ylidene in THF. Both complexes were fully characterized by 1H NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Variable temperature 1H NMR studies and X-ray crystallographic analysis revealed that intramolecular π-π stacking interactions may play a notable role in stabilizing 2, thereby rendering it the thermodynamically favored species, consistent with the Gibbs free energy study obtained from DFT calculations. Both complexes displayed weak emission with λmax around 610 nm. To elucidate the underlying electronic structure and photophysical behavior, cyclic voltammetry and DFT/TDDFT computational studies were also conducted, providing insights into the observed optical properties.
{"title":"Cyclometalated iridium(III)–Salen NHC complexes: Gibbs energy–driven isomer distribution, structures, and Photophysical properties","authors":"Daqing Chen, Chenghui Han","doi":"10.1016/j.ica.2025.122961","DOIUrl":"10.1016/j.ica.2025.122961","url":null,"abstract":"<div><div>Two isomeric cyclometalated iridium(III) N-heterocyclic carbene (NHC) complexes (<strong>1</strong> and <strong>2</strong>) bearing a salen ligand were synthesized by treating the [Ir<sup>III</sup>-salen-(Cl)(CO)] precursor with 1-phenyl-3-methylimidazol-2-ylidene in THF. Both complexes were fully characterized by <sup>1</sup>H NMR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Variable temperature <sup>1</sup>H NMR studies and X-ray crystallographic analysis revealed that intramolecular π-π stacking interactions may play a notable role in stabilizing <strong>2</strong>, thereby rendering it the thermodynamically favored species, consistent with the Gibbs free energy study obtained from DFT calculations. Both complexes displayed weak emission with λ<sub>max</sub> around 610 nm. To elucidate the underlying electronic structure and photophysical behavior, cyclic voltammetry and DFT/TDDFT computational studies were also conducted, providing insights into the observed optical properties.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122961"},"PeriodicalIF":3.2,"publicationDate":"2025-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145335182","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 : 2025-10-17DOI: 10.1016/j.ica.2025.122958
Reyaz Ahmad, Mukesh Choudhary
The synthesis and theoretical/biological evaluation of a novel Cu(II) complex [Cu(L)2]n(1) (where L is synthesized ligand) intended as a dual function agent against SARS-CoV-2 Mpro and cancer cells, is described. The complex was extensively characterized using single-crystal X-ray diffraction and spectroscopic methods as well as computational approaches. Single-crystal X-ray structure of Cu(II) complex [Cu(L)2]n(1) revealed that the coordination geometry around Cu(II) ion is distorted octahedral. The cytotoxicity activity (anticancer efficacy) of the complex was investigated on HeLa and A549 cancer cells by the MTT assay. The Cu(II) complex [Cu(L)2]n(1) showed moderate cytotoxicity against HeLa and A549 cells with IC50 values of 24.65 ± 0.11 μM and 27.34 ± 1.10 μM, respectively, at 24 h of incubation, when compared with the cisplatin under identical conditions gave IC50 values of 10.31 ± 1.63 μM (HeLa) and 11.45 ± 1.51 μM (A549), confirming that our complex is moderately active relative to the standard. To explore potential SARS-CoV-2 drug, we have also examined the molecular docking and MD simulation study of the Cu(II) complex [Cu(L)2]n(1) with the structure of the SARS-CoV-2 main protease (Mpro) Lambda (G15S) in complex with Nirmatrelvir (PDB ID: 7U28). The docking studies showed that Cu(II) complex had stronger binding affinity against SARS-CoV-2 Mpro. Strong hydrogen bond and hydrophobic interactions stabilized Cu(II) complex during the 100 ns simulation time with no significant fluctuation in the RMSD. Our work provides theoretical evidence that Cu(II) complex [Cu(L)2]n(1) can be developed as antiviral drug candidate against SARS-CoV-2 Mpro.
{"title":"Copper(II) complex as SARS-CoV-2 Nirmatrelvir inhibitor: Synthesis, crystal structure, anticancer and antiviral properties","authors":"Reyaz Ahmad, Mukesh Choudhary","doi":"10.1016/j.ica.2025.122958","DOIUrl":"10.1016/j.ica.2025.122958","url":null,"abstract":"<div><div>The synthesis and theoretical/biological evaluation of a novel Cu(II) complex [Cu(L)<sub>2</sub>]<sub>n</sub>(<strong>1</strong>) (where L is synthesized ligand) intended as a dual function agent against SARS-CoV-2 M<sup>pro</sup> and cancer cells, is described. The complex was extensively characterized using single-crystal X-ray diffraction and spectroscopic methods as well as computational approaches. Single-crystal X-ray structure of Cu(II) complex [Cu(L)<sub>2</sub>]<sub>n</sub>(<strong>1</strong>) revealed that the coordination geometry around Cu(II) ion is distorted octahedral. The cytotoxicity activity (anticancer efficacy) of the complex was investigated on HeLa and A549 cancer cells by the MTT assay. The Cu(II) complex [Cu(L)<sub>2</sub>]<sub>n</sub>(<strong>1</strong>) showed moderate cytotoxicity against HeLa and A549 cells with IC<sub>50</sub> values of 24.65 ± 0.11 μM and 27.34 ± 1.10 μM, respectively, at 24 h of incubation, when compared with the cisplatin under identical conditions gave IC<sub>50</sub> values of 10.31 ± 1.63 μM (HeLa) and 11.45 ± 1.51 μM (A549), confirming that our complex is moderately active relative to the standard. To explore potential SARS-CoV-2 drug, we have also examined the molecular docking and MD simulation study of the Cu(II) complex [Cu(L)<sub>2</sub>]<sub>n</sub>(<strong>1</strong>) with the structure of the SARS-CoV-2 main protease (M<sup>pro</sup>) Lambda (G15S) in complex with <em>Nirmatrelvir</em> (PDB ID: <span><span>7U28</span><svg><path></path></svg></span>). The docking studies showed that Cu(II) complex had stronger binding affinity against SARS-CoV-2 M<sup>pro</sup>. Strong hydrogen bond and hydrophobic interactions stabilized Cu(II) complex during the 100 ns simulation time with no significant fluctuation in the RMSD. Our work provides theoretical evidence that Cu(II) complex [Cu(L)<sub>2</sub>]<sub>n</sub>(<strong>1</strong>) can be developed as antiviral drug candidate against SARS-CoV-2 M<sup>pro</sup>.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122958"},"PeriodicalIF":3.2,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145361029","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 : 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":"2025-10-17","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 : 2025-10-15DOI: 10.1016/j.ica.2025.122957
Hani Nasser Abdelhamid , Walid Sharmoukh , Fakiha El-Taib Heakal , Ali Bumajdad , Mousa K. Abu-Arabi , Ramzi Maalej , Mohamed Awed , Amany S. Hegazy , Amany M. Hamad , Heba M. Fahmy
This paper describes the production and assessment of strontium titanate (SrTiO3) and its nitrogen-doped variants (denoted as SrTiO3_NH4Cl and SrTiO3_(NH4)3PO4 for materials synthesised using NH4Cl and (NH4)3PO4 as nitrogen source, respectively) as photocatalysts for the degradation of organic dyes in aqueous solutions. Transmission and scanning electron microscopies (TEM and SEM) investigations indicated that the materials exhibit dense particles averaging approximately 200 nm, with high crystallinity according to X-ray diffraction (XRD) and selected area electron diffraction (SAED). Optical investigations utilizing Tauc's plots demonstrated a consistent decrease in the band gap from 3.2 to 3.4 eV (SrTiO3) to 2.8–3.0 eV (SrTiO3_NH4Cl) and 2.5–2.8 eV (SrTiO3_(NH4)3PO4), facilitating improved absorption of visible light. The narrowing of the band gap was corroborated by the observed color transition of the powders, shifting from white for pure SrTiO3 to black for SrTiO3_(NH4)3PO4. The photocatalytic activities were evaluated utilizing methylene blue (MB) and congo red (CR) as model dyes at high concentrations (1000 ppm). In the presence of H2O2 and light, SrTiO3, SrTiO3_NH4Cl, and SrTiO3_(NH4)3PO4 attained around 80 %, 77 %, and 80 % degradation of MB within 10 min, respectively. Photocatalytic degradation of CR was observed, nearly 3 times higher than adsorption or light-only. Supplementary electrochemical investigations, encompassing photocurrent response, chronoamperometry, chronopotentiometry, and linear sweep voltammetry, further substantiated the improved charge transfer kinetics and photocatalytic efficacy of the nitrogen-doped materials. Significantly, recyclability assessments verified consistent performance over 5 consecutive cycles, indicating strong structural and photocatalytic stability.
本文介绍了钛酸锶（SrTiO3）及其氮掺杂衍生物(分别为SrTiO3_NH4Cl和SrTiO3_（NH4)3PO4，用于以NH4Cl和（NH4）3PO4为氮源合成的材料）作为降解水溶液中有机染料的光催化剂的生产和评价。透射电镜（TEM）和扫描电镜（SEM）研究表明，材料表现出平均约200 nm的致密颗粒，x射线衍射（XRD）和选择面积电子衍射（SAED）显示出较高的结晶度。利用tac图的光学研究表明，带隙从3.2 ~ 3.4 eV （SrTiO3）持续减小到2.8 ~ 3.0 eV （SrTiO3_NH4Cl）和2.5 ~ 2.8 eV (SrTiO3_(NH4)3PO4)，促进了可见光的吸收。带隙的缩小通过观察到的粉末颜色转变得到证实，从纯SrTiO3的白色到SrTiO3_(NH4)3PO4的黑色。以亚甲基蓝（MB）和刚果红（CR）为模型染料，在高浓度（1000ppm）下进行了光催化活性评价。在H2O2和光照条件下，SrTiO3、SrTiO3_NH4Cl和SrTiO3_(NH4)3PO4在10 min内对MB的降解率分别达到80%、77%和80%左右。光催化降解CR的效果比单纯吸附或光催化降解效果高近3倍。补充的电化学研究，包括光电流响应、计时安培法、计时电位法和线性扫描伏安法，进一步证实了氮掺杂材料的电荷转移动力学和光催化效率的改善。值得注意的是，可回收性评估验证了连续5次循环的一致性能，表明具有很强的结构和光催化稳定性。
{"title":"Nitrogen-doped strontium titanate (SrTiO3) perovskites for water treatment","authors":"Hani Nasser Abdelhamid , Walid Sharmoukh , Fakiha El-Taib Heakal , Ali Bumajdad , Mousa K. Abu-Arabi , Ramzi Maalej , Mohamed Awed , Amany S. Hegazy , Amany M. Hamad , Heba M. Fahmy","doi":"10.1016/j.ica.2025.122957","DOIUrl":"10.1016/j.ica.2025.122957","url":null,"abstract":"<div><div>This paper describes the production and assessment of strontium titanate (SrTiO<sub>3</sub>) and its nitrogen-doped variants (denoted as SrTiO<sub>3</sub>_NH<sub>4</sub>Cl and SrTiO<sub>3</sub>_(NH<sub>4</sub>)<sub>3</sub>PO<sub>4</sub> for materials synthesised using NH<sub>4</sub>Cl and (NH<sub>4</sub>)<sub>3</sub>PO<sub>4</sub> as nitrogen source<sub><sub>,</sub></sub> respectively) as photocatalysts for the degradation of organic dyes in aqueous solutions. Transmission and scanning electron microscopies (TEM and SEM) investigations indicated that the materials exhibit dense particles averaging approximately 200 nm, with high crystallinity according to X-ray diffraction (XRD) and selected area electron diffraction (SAED). Optical investigations utilizing Tauc's plots demonstrated a consistent decrease in the band gap from 3.2 to 3.4 eV (SrTiO<sub>3</sub>) to 2.8–3.0 eV (SrTiO<sub>3</sub>_NH<sub>4</sub>Cl) and 2.5–2.8 eV (SrTiO<sub>3</sub>_(NH<sub>4</sub>)<sub>3</sub>PO<sub>4</sub>), facilitating improved absorption of visible light. The narrowing of the band gap was corroborated by the observed color transition of the powders, shifting from white for pure SrTiO<sub>3</sub> to black for SrTiO<sub>3</sub>_(NH<sub>4</sub>)<sub>3</sub>PO<sub>4</sub>. The photocatalytic activities were evaluated utilizing methylene blue (MB) and congo red (CR) as model dyes at high concentrations (1000 ppm). In the presence of H<sub>2</sub>O<sub>2</sub> and light, SrTiO<sub>3</sub>, SrTiO<sub>3</sub>_NH<sub>4</sub>Cl, and SrTiO<sub>3</sub>_(NH<sub>4</sub>)<sub>3</sub>PO<sub>4</sub> attained around 80 %, 77 %, and 80 % degradation of MB within 10 min, respectively. Photocatalytic degradation of CR was observed, nearly 3 times higher than adsorption or light-only. Supplementary electrochemical investigations, encompassing photocurrent response, chronoamperometry, chronopotentiometry, and linear sweep voltammetry, further substantiated the improved charge transfer kinetics and photocatalytic efficacy of the nitrogen-doped materials. Significantly, recyclability assessments verified consistent performance over 5 consecutive cycles, indicating strong structural and photocatalytic stability.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122957"},"PeriodicalIF":3.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145333365","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 : 2025-10-15DOI: 10.1016/j.ica.2025.122950
Helen C. Aspinall
This article uses concepts of symmetry and group theory that are familiar to the inorganic chemist to explain some of the theory of the ancient (4 centuries old) practice of change ringing on church bells. The algorithms that are used by change ringers to enable them to ring all possible permutations on n bells are known as ‘methods’, and every element in the Periodic Table gives its name to at least one method. Of all these ‘elemental methods’, the most performed is Ytterbium Surprise Major – hence providing a link between rare earth chemistry and culture.
{"title":"Ytterbium Surprise – the meeting of a rare earth element with symmetry, group theory and culture","authors":"Helen C. Aspinall","doi":"10.1016/j.ica.2025.122950","DOIUrl":"10.1016/j.ica.2025.122950","url":null,"abstract":"<div><div>This article uses concepts of symmetry and group theory that are familiar to the inorganic chemist to explain some of the theory of the ancient (4 centuries old) practice of change ringing on church bells. The algorithms that are used by change ringers to enable them to ring all possible permutations on <em>n</em> bells are known as ‘methods’, and every element in the Periodic Table gives its name to at least one method. Of all these ‘elemental methods’, the most performed is Ytterbium Surprise Major – hence providing a link between rare earth chemistry and culture.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122950"},"PeriodicalIF":3.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145333359","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 : 2025-10-15DOI: 10.1016/j.ica.2025.122955
Dheeraj , Lata Rana , Kuldeep Mahiya
Four copper(II) complexes i.e. [Cu(L1–4)2] (1–4), derived from Schiff base ligands, were synthesized along with their functionalized reduced graphene oxide (rGO)-anchored counterparts as [Cu(L1–4)2]@rGO (5–8). Among these, complex 3 was unequivocally characterized by single-crystal X-ray diffraction, which revealed a square-planar geometry around the copper center. Both the homogeneous and rGO-supported complexes were evaluated as catalysts for hetero-Diels–Alder (HDA) cycloaddition reactions. In this transformation, aromatic primary amines such as aniline underwent oxidation in the presence of hydrogen peroxide and the copper catalysts to generate reactive nitroso intermediates. These intermediates readily participated in cycloaddition with 1,3-cyclohexadiene, furnishing oxazine derivatives in good yields and with shorter reaction times compared to previously reported protocols. The rGO-immobilized catalysts could be readily separated from the reaction mixture and reused for up to four consecutive cycles with negligible loss in activity. Owing to their high thermal robustness, recyclability, and efficiency, these catalysts provide a practical and sustainable route for the synthesis of oxazine derivatives.
{"title":"Efficient hetero-diels-alder reactions catalyzed by copper(II) complexes immobilized on reduced graphene oxide","authors":"Dheeraj , Lata Rana , Kuldeep Mahiya","doi":"10.1016/j.ica.2025.122955","DOIUrl":"10.1016/j.ica.2025.122955","url":null,"abstract":"<div><div>Four copper(II) complexes i.e. [Cu(L<sup>1–4</sup>)<sub>2</sub>] (<strong>1–4</strong>), derived from Schiff base ligands, were synthesized along with their functionalized reduced graphene oxide (rGO)-anchored counterparts as [Cu(L<sup>1–4</sup>)<sub>2</sub>]@rGO (<strong>5–8</strong>). Among these, complex <strong>3</strong> was unequivocally characterized by single-crystal X-ray diffraction, which revealed a square-planar geometry around the copper center. Both the homogeneous and rGO-supported complexes were evaluated as catalysts for hetero-Diels–Alder (HDA) cycloaddition reactions. In this transformation, aromatic primary amines such as aniline underwent oxidation in the presence of hydrogen peroxide and the copper catalysts to generate reactive nitroso intermediates. These intermediates readily participated in cycloaddition with 1,3-cyclohexadiene, furnishing oxazine derivatives in good yields and with shorter reaction times compared to previously reported protocols. The rGO-immobilized catalysts could be readily separated from the reaction mixture and reused for up to four consecutive cycles with negligible loss in activity. Owing to their high thermal robustness, recyclability, and efficiency, these catalysts provide a practical and sustainable route for the synthesis of oxazine derivatives.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122955"},"PeriodicalIF":3.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145333363","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 : 2025-10-15DOI: 10.1016/j.ica.2025.122951
Yanqiu Zhang , Sijia Jin , Xu-Dong Zhao , Hou Wang , Chong-Chen Wang
{"title":"Advances in MOFs for environmental applications","authors":"Yanqiu Zhang , Sijia Jin , Xu-Dong Zhao , Hou Wang , Chong-Chen Wang","doi":"10.1016/j.ica.2025.122951","DOIUrl":"10.1016/j.ica.2025.122951","url":null,"abstract":"","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122951"},"PeriodicalIF":3.2,"publicationDate":"2025-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145424379","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}
Zinc is an essential transition metal ion in our body system. Its deficiency and deposition lead to several health issues. Thus, its detection becomes necessary. For this purpose, we have synthesized a bisphenol A derivative (H2L-Oxy) incorporating a pyridine unit as a chemosensor by a two-step reaction for detection of Zn2+. The probe exhibited a weak emission band at 530 nm in 10 mM HEPES buffer in H2O/DMF = 4: 1 (v/v) (pH 7.4) when it was excited at 410 nm. While in the presence of Zn2+, the fluorescence intensity of H₂L-Oxy increased by 12 times at 467 nm with a blue shift of 54 nm. This enhancement of fluorescence intensity has been explained by the restriction of CN isomerization, ICT (Intramolecular charge transfer) and CHEF (Chelation enhancement of fluorescence) mechanism. The limit of detection (LOD) of the probe towards the cation was determined as 5.53 × 10−8 M. H2L-Oxy formed a 1: 2 complex with Zn2+ with an association constant of 1.7 × 104 M- 1. Theoretical calculations have been carried out to support the observed results. It has been applied in imaging of Zn2+ in living cells.
{"title":"A bisphenol A based selective and biocompatible chemosensor for zinc ion","authors":"Shephali Mahato , Tiasha Dutta , Sushil Kumar Mandal , Pritam Ghosh , Partha Roy","doi":"10.1016/j.ica.2025.122952","DOIUrl":"10.1016/j.ica.2025.122952","url":null,"abstract":"<div><div>Zinc is an essential transition metal ion in our body system. Its deficiency and deposition lead to several health issues. Thus, its detection becomes necessary. For this purpose, we have synthesized a bisphenol A derivative (H<sub>2</sub>L-Oxy) incorporating a pyridine unit as a chemosensor by a two-step reaction for detection of Zn<sup>2+</sup>. The probe exhibited a weak emission band at 530 nm in 10 mM HEPES buffer in H<sub>2</sub>O/DMF = 4: 1 (<em>v</em>/v) (pH 7.4) when it was excited at 410 nm. While in the presence of Zn<sup>2+</sup>, the fluorescence intensity of H₂L-Oxy increased by 12 times at 467 nm with a blue shift of 54 nm. This enhancement of fluorescence intensity has been explained by the restriction of <img>C<img>N isomerization, ICT (Intramolecular charge transfer) and CHEF (Chelation enhancement of fluorescence) mechanism. The limit of detection (LOD) of the probe towards the cation was determined as 5.53 × 10<sup>−8</sup> M. H<sub>2</sub>L-Oxy formed a 1: 2 complex with Zn<sup>2+</sup> with an association constant of 1.7 × 10<sup>4</sup> M<sup>- 1</sup>. Theoretical calculations have been carried out to support the observed results. It has been applied in imaging of Zn<sup>2+</sup> in living cells.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122952"},"PeriodicalIF":3.2,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145333388","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 : 2025-10-14DOI: 10.1016/j.ica.2025.122956
Milica Međedović Stefanović , Nevenka Gligorijević , Asmet N. Azizova , Dejan Milenković , Milan Vraneš , Nenad Janković , Biljana Petrović , Ghodrat Mahmoudi , Ana Rilak Simović
This study presents the synthesis and comprehensive characterization of four novel Ru(II) polypyridyl complexes with the general formula mer-[Ru(L)(NN)Cl]Cl, where L represents a 4′-substituted terpyridine ligand (2-thienyl or 2-furyl derivatives), and NN denotes either 2,2′-bipyridine (complexes 1 and 3) or 1,10-phenanthroline (complexes 2 and 4). Parallel synthesis of three biocompatible ionic liquids (Bio-ILs) 2-hydroxypropan-1-ammonium lactate (IL1), oxalate (IL2), and citrate (IL3) was achieved with high yields. The Ru(II) complexes were fully characterized by elemental analysis, IR, UV–Vis, 1H/13C NMR, and ESI-MS spectroscopy, confirming their structures and purity. Kinetic studies with guanosine-5′-monophosphate (5′-GMP) and L-cysteine (L-Cys) revealed ligand substitution reactivity in the order 2 > 1 > 4 > 3, influenced by both ligand electronics and nucleophile identity. DNA binding assays using ethidium bromide and Hoechst 33258 showed that all complexes interact with calf thymus DNA via partial intercalation and minor groove binding. Human serum albumin (HSA) binding studies using site-specific probes (eosin Y for site I, ibuprofen for site II) confirmed strong affinity (Kb = 104–105 M−1) for both sites. Notably, Bio-ILs enhanced DNA/HSA binding affinities in the order: PBS < IL1 < IL2 < IL3, attributed to increased solvent polarity. Molecular docking supported the DNA/HSA experimental interaction profiles. Cytotoxicity evaluation via MTT assay on various human cancer cell lines identified complex 3 as the most potent and selective in HeLa cells. However, mechanistic studies indicated that complex 3 did not induce apoptosis or affect cell cycle progression, suggesting a non-classical mode of action.
{"title":"Heteroaryl-Terpyridine ruthenium(II) complexes in biocompatible ionic liquids: Synthesis, structural characterization, computational and biological evaluation","authors":"Milica Međedović Stefanović , Nevenka Gligorijević , Asmet N. Azizova , Dejan Milenković , Milan Vraneš , Nenad Janković , Biljana Petrović , Ghodrat Mahmoudi , Ana Rilak Simović","doi":"10.1016/j.ica.2025.122956","DOIUrl":"10.1016/j.ica.2025.122956","url":null,"abstract":"<div><div>This study presents the synthesis and comprehensive characterization of four novel Ru(II) polypyridyl complexes with the general formula <em>mer</em>-[Ru(L)(<em>N<img>N</em>)Cl]Cl, where L represents a 4′-substituted terpyridine ligand (2-thienyl or 2-furyl derivatives), and <em>N<img>N</em> denotes either 2,2′-bipyridine (complexes <strong>1</strong> and <strong>3</strong>) or 1,10-phenanthroline (complexes <strong>2</strong> and <strong>4</strong>). Parallel synthesis of three biocompatible ionic liquids (Bio-ILs) 2-hydroxypropan-1-ammonium lactate (IL1), oxalate (IL2), and citrate (IL3) was achieved with high yields. The Ru(II) complexes were fully characterized by elemental analysis, IR, UV–Vis, <sup>1</sup>H/<sup>13</sup>C NMR, and ESI-MS spectroscopy, confirming their structures and purity. Kinetic studies with guanosine-5′-monophosphate (5′-GMP) and L-cysteine (L-Cys) revealed ligand substitution reactivity in the order <strong>2</strong> > <strong>1</strong> > <strong>4</strong> > <strong>3</strong>, influenced by both ligand electronics and nucleophile identity. DNA binding assays using ethidium bromide and Hoechst 33258 showed that all complexes interact with calf thymus DNA <em>via</em> partial intercalation and minor groove binding. Human serum albumin (HSA) binding studies using site-specific probes (eosin Y for site I, ibuprofen for site II) confirmed strong affinity (<em>K</em><sub>b</sub> = 10<sup>4</sup>–10<sup>5</sup> M<sup>−1</sup>) for both sites. Notably, Bio-ILs enhanced DNA/HSA binding affinities in the order: PBS < IL1 < IL2 < IL3, attributed to increased solvent polarity. Molecular docking supported the DNA/HSA experimental interaction profiles. Cytotoxicity evaluation <em>via</em> MTT assay on various human cancer cell lines identified complex <strong>3</strong> as the most potent and selective in HeLa cells. However, mechanistic studies indicated that complex <strong>3</strong> did not induce apoptosis or affect cell cycle progression, suggesting a non-classical mode of action.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"589 ","pages":"Article 122956"},"PeriodicalIF":3.2,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145358476","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 : 2025-10-12DOI: 10.1016/j.ica.2025.122953
Yufei Xie , Howard Z. Ma , Allan J. Canty , Richard A.J. O'Hair
Multistage mass spectrometry (MSn) experiments using a linear ion trap mass spectrometer in conjunction with density functional theory (DFT) calculations have been employed to determine the fragmentation pathways for the thermal decomposition of alkali metal perfluoropropionate complexes. Electrospray ionisation (ESI) in the negative ion mode was used to generate the precursor complexes, [CF3CF2CO2MO2CCF2CF3]− (M = Li, Na and K) in the gas phase. Upon collision-induced dissociation (CID) a minor amount of CF3CF2CO2− formation was observed, consistent with DFT calculations which predict strong binding energies of the carboxylate to the metal centres (ΔH° calculated to be 50.8, 47.9 and 44.3 kcal/mol for M = Li, Na and K, respectively). The major fragmentation pathway involved formation of the fluoride complexes [CF3CF2CO2MF]− via the loss of “C2F4CO2”.
The organometallic complex [CF3CF2CO2MCF2CF3]− formed via decarboxylation, although a minor pathway in all cases, was formed in sufficient yield to allow it to be mass selected to study its further fragmentation pathways. The dominant pathway for the fragmentation of the organometallic complexes [CF3CF2CO2MCF2CF3]− involves formation of the fluoride complexes [CF3CF2CO2MF]− in all cases, and DFT calculations reveal a facile β‑fluorine elimination pathway process with low barriers (21.9, 22.1 and 21.8 kcal/mol for M = Li, Na and K, respectively). The fluoride complexes [CF3CF2CO2MF]− fragment via decarboxylation to give [CF3CF2MF]− in competition with CF3CF2CO2− formation. DFT calculations were carried out to explore potentially competing mechanisms for loss of “C2F4CO2” including: concerted or stepwise loss of CO2 and CF2CF2 and a CF2CF2CO2 lactone pathway. While the loss of lactone pathway has the lower overall energy barrier, the combined loss of CO2 and CF2 = CF2 maybe the likely pathway since decarboxylation is easily followed by β-fluoride elimination. In addition, the possibility of forming [CF3CF2MCF2CF3]− and [CF3CF2MF]−, via decarboxylation is discussed. Finally, the fluoride complexes [FMF]− M = Na and K were experimentally observed.
{"title":"Alkali metal-mediated decarboxylation and CF activation reactions for the decomposition of perfluoropropionate into perfluoroethene.","authors":"Yufei Xie , Howard Z. Ma , Allan J. Canty , Richard A.J. O'Hair","doi":"10.1016/j.ica.2025.122953","DOIUrl":"10.1016/j.ica.2025.122953","url":null,"abstract":"<div><div>Multistage mass spectrometry (MS<sup>n</sup>) experiments using a linear ion trap mass spectrometer in conjunction with density functional theory (DFT) calculations have been employed to determine the fragmentation pathways for the thermal decomposition of alkali metal perfluoropropionate complexes. Electrospray ionisation (ESI) in the negative ion mode was used to generate the precursor complexes, [CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub>MO<sub>2</sub>CCF<sub>2</sub>CF<sub>3</sub>]<sup>−</sup> (M = Li, Na and K) in the gas phase. Upon collision-induced dissociation (CID) a minor amount of CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub><sup>−</sup> formation was observed, consistent with DFT calculations which predict strong binding energies of the carboxylate to the metal centres (Δ<em>H</em>° calculated to be 50.8, 47.9 and 44.3 kcal/mol for M = Li, Na and K, respectively). The major fragmentation pathway involved formation of the fluoride complexes [CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub>MF]<sup>−</sup> via the loss of “C<sub>2</sub>F<sub>4</sub>CO<sub>2</sub>”.</div><div>The organometallic complex [CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub>MCF<sub>2</sub>CF<sub>3</sub>]<sup>−</sup> formed via decarboxylation, although a minor pathway in all cases, was formed in sufficient yield to allow it to be mass selected to study its further fragmentation pathways. The dominant pathway for the fragmentation of the organometallic complexes [CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub>MCF<sub>2</sub>CF<sub>3</sub>]<sup>−</sup> involves formation of the fluoride complexes [CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub>MF]<sup>−</sup> in all cases, and DFT calculations reveal a facile β‑fluorine elimination pathway process with low barriers (21.9, 22.1 and 21.8 kcal/mol for M = Li, Na and K, respectively). The fluoride complexes [CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub>MF]<sup>−</sup> fragment via decarboxylation to give [CF<sub>3</sub>CF<sub>2</sub>MF]<sup>−</sup> in competition with CF<sub>3</sub>CF<sub>2</sub>CO<sub>2</sub><sup>−</sup> formation. DFT calculations were carried out to explore potentially competing mechanisms for loss of “C<sub>2</sub>F<sub>4</sub>CO<sub>2</sub>” including: concerted or stepwise loss of CO<sub>2</sub> and CF<sub>2</sub><img>CF<sub>2</sub> and a CF<sub>2</sub>CF<sub>2</sub>CO<sub>2</sub> lactone pathway. While the loss of lactone pathway has the lower overall energy barrier, the combined loss of CO<sub>2</sub> and CF<sub>2</sub> = CF<sub>2</sub> maybe the likely pathway since decarboxylation is easily followed by β-fluoride elimination. In addition, the possibility of forming [CF<sub>3</sub>CF<sub>2</sub>MCF<sub>2</sub>CF<sub>3</sub>]<sup>−</sup> and [CF<sub>3</sub>CF<sub>2</sub>MF]<sup>−</sup>, via decarboxylation is discussed. Finally, the fluoride complexes [FMF]<sup>−</sup> M = Na and K were experimentally observed.</div></div>","PeriodicalId":13599,"journal":{"name":"Inorganica Chimica Acta","volume":"590 ","pages":"Article 122953"},"PeriodicalIF":3.2,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145419058","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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