Pub Date : 2026-02-02DOI: 10.1016/j.jorganchem.2026.124053
Mitat Akkoç , Belgin Önder , Enes Evren , Emine Özge Karaca , Nevin Gürbüz , İsmail Özdemir
This study reports the synthesis of novel N-heterocyclic carbene (NHC) ligated silver(I) complexes, which are gaining increasing attention as versatile catalysts in organic synthesis. The structural properties of the synthesized compounds were elucidated in detail using various spectroscopic and thermal analysis techniques, including FTIR, NMR spectroscopy, and melting point determination. These analyses confirmed the successful formation of the complexes and verified that they exhibited the expected molecular structures. The low cost and unique chemical properties of silver make it an attractive alternative to other transition metals. In this context, the catalytic potential of the synthesized Ag-NHC complexes was investigated in the A³ coupling reaction, a key method for the synthesis of propargylamines. The A³ reaction is a crucial step in the formation of nitrogen-containing compounds of significant importance in pharmaceutical and natural product chemistry. Experimental results demonstrated that the Ag-NHC complexes effectively catalyzed the reaction, leading to high yields. In conclusion, this research successfully achieved the synthesis and characterization of new Ag-NHC complexes. Following the acquisition of structural analysis data, their catalytic activity in the A³ coupling reaction was successfully investigated.
{"title":"Systematic study on the catalytic performance of NHC-ligated silver(I) complexes","authors":"Mitat Akkoç , Belgin Önder , Enes Evren , Emine Özge Karaca , Nevin Gürbüz , İsmail Özdemir","doi":"10.1016/j.jorganchem.2026.124053","DOIUrl":"10.1016/j.jorganchem.2026.124053","url":null,"abstract":"<div><div>This study reports the synthesis of novel N-heterocyclic carbene (NHC) ligated silver(I) complexes, which are gaining increasing attention as versatile catalysts in organic synthesis. The structural properties of the synthesized compounds were elucidated in detail using various spectroscopic and thermal analysis techniques, including FTIR, NMR spectroscopy, and melting point determination. These analyses confirmed the successful formation of the complexes and verified that they exhibited the expected molecular structures. The low cost and unique chemical properties of silver make it an attractive alternative to other transition metals. In this context, the catalytic potential of the synthesized Ag-NHC complexes was investigated in the A³ coupling reaction, a key method for the synthesis of propargylamines. The A³ reaction is a crucial step in the formation of nitrogen-containing compounds of significant importance in pharmaceutical and natural product chemistry. Experimental results demonstrated that the Ag-NHC complexes effectively catalyzed the reaction, leading to high yields. In conclusion, this research successfully achieved the synthesis and characterization of new Ag-NHC complexes. Following the acquisition of structural analysis data, their catalytic activity in the A³ coupling reaction was successfully investigated.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1049 ","pages":"Article 124053"},"PeriodicalIF":2.1,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122698","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 : 2026-01-28DOI: 10.1016/j.jorganchem.2026.124042
Jia Ji , Xuan Lv , Wen-Qian Deng , Lin Tian , Teng-Qi Yao , Wen-Jing Shi , Da-Hui Wang , Qing Li , Yin-Ling Hou , Ming Fang
Herein, two tetranuclear Ni(II)-based compounds formulated as [Ni4(L1)4(CH3OH)4] (1) and [Ni4(L2)4(CH3OH)4] (2) (H2L1 = (E)-4‑bromo-2-(((5‑chloro-2-(hydroxymethyl)phenyl)imino)methyl)phenol, and H2L2 = (E)-4‑bromo-2-(((2-(hydroxymethyl)phenyl)imino)methyl)phenol) have been obtained by using two different Schiff-base ligands via solvothermal method. Single crystal X-ray diffraction analysis shows that the structures of the two tetranuclear compounds (1 and 2) are mainly composed of four Ni(II) ions, four L12-/L22-, and four coordinated CH3OH, and the four central Ni(II) ions are bridged by four μ3O atoms forming a cubane Ni4O4 core. Notably, compounds 1 and 2 exhibit outstanding catalytic performance for the cycloaddition of CO2 and epoxides under mild conditions. Among them, compound 1 exhibit the highest catalytic efficiency for substrate 2-(bromomethyl)oxirane, with a corresponding yield of up to 98 %; while for substrate 2-(tert‑butoxymethyl)oxirane, which shows relatively lower catalytic activity, the yield can still reach 84 %. What's more, compound 1 as heterogenous catalyst can be reused at least five times without obvious loss in catalytic activity for the cycloaddition reaction.
{"title":"Two tetranuclear Ni(II)-based compounds with a cubane Ni4O4 core: Efficient conversion of CO2 to cyclic carbonates","authors":"Jia Ji , Xuan Lv , Wen-Qian Deng , Lin Tian , Teng-Qi Yao , Wen-Jing Shi , Da-Hui Wang , Qing Li , Yin-Ling Hou , Ming Fang","doi":"10.1016/j.jorganchem.2026.124042","DOIUrl":"10.1016/j.jorganchem.2026.124042","url":null,"abstract":"<div><div>Herein, two tetranuclear Ni(II)-based compounds formulated as [Ni<sub>4</sub>(L<sub>1</sub>)<sub>4</sub>(CH<sub>3</sub>OH)<sub>4</sub>] (<strong>1</strong>) and [Ni<sub>4</sub>(L<sub>2</sub>)<sub>4</sub>(CH<sub>3</sub>OH)<sub>4</sub>] (<strong>2</strong>) (H<sub>2</sub>L<sub>1</sub> = (E)-4‑bromo-2-(((5‑chloro-2-(hydroxymethyl)phenyl)imino)methyl)phenol, and H<sub>2</sub>L<sub>2</sub> = (E)-4‑bromo-2-(((2-(hydroxymethyl)phenyl)imino)methyl)phenol) have been obtained by using two different Schiff-base ligands via solvothermal method. Single crystal X-ray diffraction analysis shows that the structures of the two tetranuclear compounds (<strong>1</strong> and <strong>2)</strong> are mainly composed of four Ni(II) ions, four L<sub>1</sub><sup>2-</sup>/L<sub>2</sub><sup>2-</sup>, and four coordinated CH<sub>3</sub>OH, and the four central Ni(II) ions are bridged by four <em>μ</em><sub>3<img></sub>O atoms forming a cubane Ni<sub>4</sub>O<sub>4</sub> core. Notably, compounds <strong>1</strong> and <strong>2</strong> exhibit outstanding catalytic performance for the cycloaddition of CO<sub>2</sub> and epoxides under mild conditions. Among them, compound <strong>1</strong> exhibit the highest catalytic efficiency for substrate 2-(bromomethyl)oxirane, with a corresponding yield of up to 98 %; while for substrate 2-(tert‑butoxymethyl)oxirane, which shows relatively lower catalytic activity, the yield can still reach 84 %. What's more, compound <strong>1</strong> as heterogenous catalyst can be reused at least five times without obvious loss in catalytic activity for the cycloaddition reaction.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1049 ","pages":"Article 124042"},"PeriodicalIF":2.1,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122697","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 : 2026-01-25DOI: 10.1016/j.jorganchem.2026.124041
Ingo Ott
Gold complexes with N-heterocyclic carbene (NHC) ligands have been intensively studied as new anticancer agents, while other biomedical and therapeutic applications have been less frequently explored. In this review the antibacterial properties of gold NHC complexes are summarised. In particular monocarbene complexes of the type (NHC)Au(Ⅰ)Cl have demonstrated considerable antibacterial activity with preference for Gram-positive bacteria. The inhibition of bacterial thioredoxin reductase, biofilm eradication and membrane damage have been experimentally confirmed for several examples and unwanted toxicity against eukaryotic cells could be reduced by bioconjugation or formation of hybrid agents with antibiotics. In summary, gold NHC complexes represent a new type of antibacterial agent with promising potential for antibiotic drug development.
{"title":"Recent developments on gold N-heterocyclic carbene complexes as antibacterial tool compounds and potential antibiotics","authors":"Ingo Ott","doi":"10.1016/j.jorganchem.2026.124041","DOIUrl":"10.1016/j.jorganchem.2026.124041","url":null,"abstract":"<div><div>Gold complexes with N-heterocyclic carbene (NHC) ligands have been intensively studied as new anticancer agents, while other biomedical and therapeutic applications have been less frequently explored. In this review the antibacterial properties of gold NHC complexes are summarised. In particular monocarbene complexes of the type (NHC)Au(Ⅰ)Cl have demonstrated considerable antibacterial activity with preference for Gram-positive bacteria. The inhibition of bacterial thioredoxin reductase, biofilm eradication and membrane damage have been experimentally confirmed for several examples and unwanted toxicity against eukaryotic cells could be reduced by bioconjugation or formation of hybrid agents with antibiotics. In summary, gold NHC complexes represent a new type of antibacterial agent with promising potential for antibiotic drug development.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124041"},"PeriodicalIF":2.1,"publicationDate":"2026-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076034","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 : 2026-01-23DOI: 10.1016/j.jorganchem.2026.124033
Yingqiao Wang , Ruitao Feng , Yilan Jin , Hong Yang , Xu Chen
α-Octabutoxy-naphthalocyanine palladium(II), denoted as PdNc(OBu)8, has been successfully synthesized. To improve water solubility and biocompatibility, we encapsulated it with bovine serum albumin (BSA) to form nanoparticles of PdNc(OBu)8 NPs. The nanoparticles show strong NIR absorption centered at 825 nm. Under 808 nm laser irradiation, PdNc(OBu)8 NPs generate both singlet oxygen (1O2) and superoxide radical (O2•−). They also act as strong photothermal agents with a photothermal conversion efficiency of ∼66%. For 4T1 cells, the NIR irradiation of PdNc(OBu)8 NPs causes marked cell death with the photothermal and type I/II photodynamic effect. All these results supported PdNc(OBu)8 NPs should be promising for combined type I/II photodynamic and photothermal cancer therapy.
{"title":"NIR-activated α-Octabutoxy-naphthalocyanine palladium(II) nanoparticles for synergistic photothermal and type Ι/II photodynamic therapy of cancer cells","authors":"Yingqiao Wang , Ruitao Feng , Yilan Jin , Hong Yang , Xu Chen","doi":"10.1016/j.jorganchem.2026.124033","DOIUrl":"10.1016/j.jorganchem.2026.124033","url":null,"abstract":"<div><div>α-Octabutoxy-naphthalocyanine palladium(II), denoted as PdNc(OBu)<sub>8</sub>, has been successfully synthesized. To improve water solubility and biocompatibility, we encapsulated it with bovine serum albumin (BSA) to form nanoparticles of PdNc(OBu)<sub>8</sub> NPs. The nanoparticles show strong NIR absorption centered at 825 nm. Under 808 nm laser irradiation, PdNc(OBu)<sub>8</sub> NPs generate both singlet oxygen (<sup>1</sup>O<sub>2</sub>) and superoxide radical (O<sub>2</sub><sup>•−</sup>). They also act as strong photothermal agents with a photothermal conversion efficiency of ∼66%. For 4T1 cells, the NIR irradiation of PdNc(OBu)<sub>8</sub> NPs causes marked cell death with the photothermal and type I/II photodynamic effect. All these results supported PdNc(OBu)<sub>8</sub> NPs should be promising for combined type I/II photodynamic and photothermal cancer therapy.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124033"},"PeriodicalIF":2.1,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076449","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}
Halogen atom transfer (XAT) reactions are fundamental in radical-mediated organic synthesis, visible-light photocatalysis, and electro-organic transformations. Accurate prediction of activation barriers is essential to mechanistic understanding and rational design of novel radical pathways. Herein, we present a systematic benchmark of 24 density functional theory (DFT) methods — including GGA, hybrid GGA, (hybrid) meta-GGA, and double-hybrid functionals — against high-level DLPNO-CCSD(T)/CBS reference energies for a diverse set of 15 representative XAT reactions involving various halogens (Cl, Br, I) and radical types. Based on our benchmarking results, we propose CAM-B3LYP-D3(BJ) as a reliable computational protocol for main-group XAT reactions in future mechanistic studies.
{"title":"Benchmarking of density functional theory calculation approaches for activation barriers in halogen atom transfer reactions","authors":"Tianyi Chen , Chaoyue Zhao , Shuoqing Zhang , Xin Hong","doi":"10.1016/j.jorganchem.2026.124013","DOIUrl":"10.1016/j.jorganchem.2026.124013","url":null,"abstract":"<div><div>Halogen atom transfer (XAT) reactions are fundamental in radical-mediated organic synthesis, visible-light photocatalysis, and electro-organic transformations. Accurate prediction of activation barriers is essential to mechanistic understanding and rational design of novel radical pathways. Herein, we present a systematic benchmark of 24 density functional theory (DFT) methods — including GGA, hybrid GGA, (hybrid) meta-GGA, and double-hybrid functionals — against high-level DLPNO-CCSD(T)/CBS reference energies for a diverse set of 15 representative XAT reactions involving various halogens (Cl, Br, I) and radical types. Based on our benchmarking results, we propose CAM-B3LYP-D3(BJ) as a reliable computational protocol for main-group XAT reactions in future mechanistic studies.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124013"},"PeriodicalIF":2.1,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076440","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 : 2026-01-19DOI: 10.1016/j.jorganchem.2026.124029
Alaa Maatouk, Thibaud Rossel, Bruno Therrien
Selective recognition of biomolecules is of paramount importance in medicine, biotechnology, and cellular biology. Adenosine triphosphate (ATP), the universal energy currency of living systems, represents a valuable analytical target in sensing technology. However, discriminating ATP from its closely related analogues (ADP, AMP) remains a challenge. Herein, we report the synthesis of two arene ruthenium metalla-rectangles incorporating urea-based units. These water-stable assemblies are obtained from the dinuclear complex [Ru2(p-cymene)2{bis(2-hydroxyethyl)oxamidate}Cl2] and the bipyridyl connectors 1,1′-(1,4-phenylene)bis{3-(pyridin-4-yl)urea} (PPU) and 1,1′-(naphthalene-1,5-diyl)bis{3-(pyridin-4-yl)urea} (NPU) in the presence of silver triflate. Both metalla-rectangles are isolated as triflate salts, with the formula [Ru4(p-cymene)4{bis(2-hydroxyethyl)oxamidate}2(PPU)2](CF3SO3)4 (MRPPU) and [Ru4(p-cymene)4{bis(2-hydroxyethyl)ethanediamide}2(NPU)2](CF3SO3)4 (MRNPU), respectively. Both metalla-rectangles can interact with fluorescein (FLU) to form weakly-fluorescent host-guest systems, resulting in discrete fluorescent indicator displacement assays (FIDA). The MRPPU rectangle shows in buffered aqueous solution a selective ATP recognition over purine nucleotides, as opposed to MRNPU, with an affinity of 2.4 × 104 M-1 and a detection limit of 22.0 μM. The dissimilar response of these two metalla-rectangles is rationalized from their molecular design, suggesting distinct binding interactions with ATP.
{"title":"Selective recognition of ATP over phosphorylated molecules in aqueous media by urea-based arene ruthenium metalla-rectangle","authors":"Alaa Maatouk, Thibaud Rossel, Bruno Therrien","doi":"10.1016/j.jorganchem.2026.124029","DOIUrl":"10.1016/j.jorganchem.2026.124029","url":null,"abstract":"<div><div>Selective recognition of biomolecules is of paramount importance in medicine, biotechnology, and cellular biology. Adenosine triphosphate (ATP), the universal energy currency of living systems, represents a valuable analytical target in sensing technology. However, discriminating ATP from its closely related analogues (ADP, AMP) remains a challenge. Herein, we report the synthesis of two arene ruthenium metalla-rectangles incorporating urea-based units. These water-stable assemblies are obtained from the dinuclear complex [Ru<sub>2</sub>(<em>p</em>-cymene)<sub>2</sub>{bis(2-hydroxyethyl)oxamidate}Cl<sub>2</sub>] and the bipyridyl connectors 1,1′-(1,4-phenylene)bis{3-(pyridin-4-yl)urea} (PPU) and 1,1′-(naphthalene-1,5-diyl)bis{3-(pyridin-4-yl)urea} (NPU) in the presence of silver triflate. Both metalla-rectangles are isolated as triflate salts, with the formula [Ru<sub>4</sub>(<em>p</em>-cymene)<sub>4</sub>{bis(2-hydroxyethyl)oxamidate}<sub>2</sub>(PPU)<sub>2</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>4</sub> (MRPPU) and [Ru<sub>4</sub>(<em>p</em>-cymene)<sub>4</sub>{bis(2-hydroxyethyl)ethanediamide}<sub>2</sub>(NPU)<sub>2</sub>](CF<sub>3</sub>SO<sub>3</sub>)<sub>4</sub> (MRNPU), respectively. Both metalla-rectangles can interact with fluorescein (FLU) to form weakly-fluorescent host-guest systems, resulting in discrete fluorescent indicator displacement assays (FIDA). The MRPPU rectangle shows in buffered aqueous solution a selective ATP recognition over purine nucleotides, as opposed to MRNPU, with an affinity of 2.4 × 10<sup>4</sup> M<sup>-1</sup> and a detection limit of 22.0 μM. The dissimilar response of these two metalla-rectangles is rationalized from their molecular design, suggesting distinct binding interactions with ATP.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124029"},"PeriodicalIF":2.1,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146037032","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}
The increasing atmospheric concentration of carbon dioxide (CO₂) has stimulated considerable interest in its chemical fixation to produce value-added products. In this study, two novel azo-Schiff base ligands were synthesized from salicylaldehyde derivatives and subsequently coordinated with palladium(II) to afford stable Pd(II) complexes. The complexes were characterized comprehensively using elemental analysis, FT-IR, UV–Vis, NMR, and high-resolution mass spectrometry (HRMS), confirming the successful formation of the desired coordination frameworks. Their catalytic performances were systematically investigated in the cycloaddition reaction of CO₂ with various epoxides under both atmospheric and high-pressure conditions. The results revealed that the Pd(II) complexes exhibit high activity and selectivity toward cyclic carbonate formation, with yields exceeding 90% under optimized conditions. The azo functionality in the Schiff base ligands was found to play a crucial role in modulating the electronic environment around the Pd(II) center, thereby enhancing catalytic efficiency. This work highlights the potential of azo-Schiff base Pd(II) complexes as promising homogeneous catalysts for sustainable CO₂ utilization and provides new insights into ligand design strategies for efficient CO₂ fixation.
{"title":"Schiff base Pd(II) complexes as efficient catalysts for CO₂ conversion to cyclic carbonates under high and atmospheric pressure","authors":"Ayşe Kazancı Dağ , Emine Aytar , Ayşegül Köse , Esin Ispir","doi":"10.1016/j.jorganchem.2026.124028","DOIUrl":"10.1016/j.jorganchem.2026.124028","url":null,"abstract":"<div><div>The increasing atmospheric concentration of carbon dioxide (CO₂) has stimulated considerable interest in its chemical fixation to produce value-added products. In this study, two novel azo-Schiff base ligands were synthesized from salicylaldehyde derivatives and subsequently coordinated with palladium(II) to afford stable Pd(II) complexes. The complexes were characterized comprehensively using elemental analysis, FT-IR, UV–Vis, NMR, and high-resolution mass spectrometry (HRMS), confirming the successful formation of the desired coordination frameworks. Their catalytic performances were systematically investigated in the cycloaddition reaction of CO₂ with various epoxides under both atmospheric and high-pressure conditions. The results revealed that the Pd(II) complexes exhibit high activity and selectivity toward cyclic carbonate formation, with yields exceeding 90% under optimized conditions. The azo functionality in the Schiff base ligands was found to play a crucial role in modulating the electronic environment around the Pd(II) center, thereby enhancing catalytic efficiency. This work highlights the potential of azo-Schiff base Pd(II) complexes as promising homogeneous catalysts for sustainable CO₂ utilization and provides new insights into ligand design strategies for efficient CO₂ fixation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124028"},"PeriodicalIF":2.1,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146024051","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 : 2026-01-19DOI: 10.1016/j.jorganchem.2026.124031
Yu-Huei Li , I-Hsuan Fu , Yen-Ming Chen , Hui-Lung Chen , Minghuey Shieh
Efficient synthetic routes to metal carbonyl cluster–based polymers via ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)2(BF4)]n, and Hg-bridged iron carbonyl chalcogenide clusters, [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)2(BF4)]n was treated with [Et4N]2[Hg{TeFe3(CO)9}2] in a ratio of 2: 1 via liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)2}2{Hg[TeFe3(CO)9]2}]n (1) was obtained. Single-crystal X-ray diffraction showed that polymer 1 consisted of cationic chains [Cu(dpy)(MeCN)2]n and weakly coordinating anions [Hg{TeFe3(CO)9}2]2–. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}2{Hg[SFe3(CO)9]2}]n (2) was formed, with the [Hg{SFe3(CO)9}2] moiety serving as a cross-linker via the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)2(BF4)]n, chalcogenide clusters [Et4N]2[Hg{EFe3(CO)9}2] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)2}2{Cu(dpy)1.5(MeCN)}2{Hg[EFe3(CO)9]2}2]n (E = Te, 3a; Se, 3b), respectively. Notably, polymer 3a could be obtained by the transformation of polymer 1 with dpy via LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers 1, 2, 3a, and 3b possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)2(BF4)]n (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.
{"title":"Cu–dipyridyl polymers incorporating weakly coordinating E–Fe–Hg–CO (E = Te, Se, S) clusters: Mechanochemical anion-exchange, cluster-induced framework transformations, and semiconducting properties","authors":"Yu-Huei Li , I-Hsuan Fu , Yen-Ming Chen , Hui-Lung Chen , Minghuey Shieh","doi":"10.1016/j.jorganchem.2026.124031","DOIUrl":"10.1016/j.jorganchem.2026.124031","url":null,"abstract":"<div><div>Efficient synthetic routes to metal carbonyl cluster–based polymers <em>via</em> ion-exchange processes remain unexplored. In this study, a mechanochemical ion-exchange strategy was developed using a one-dimensional (1D) Cu–dpy (dpy = 4,4’-dipyridyl) template polymer, [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em>, and Hg-bridged iron carbonyl chalcogenide clusters, [Et<sub>4</sub>N]<sub>2</sub>[Hg{EFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] (E = Te, Se, S), to construct novel polymeric materials. When polymer [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em> was treated with [Et<sub>4</sub>N]<sub>2</sub>[Hg{TeFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] in a ratio of 2: 1 <em>via</em> liquid-assisted grinding (LAG), a 1D polymer [{Cu(dpy)(MeCN)<sub>2</sub>}<sub>2</sub>{Hg[TeFe<sub>3</sub>(CO)<sub>9</sub>]<sub>2</sub>}]<em><sub>n</sub></em> (<strong>1</strong>) was obtained. Single-crystal X-ray diffraction showed that polymer <strong>1</strong> consisted of cationic chains [Cu(dpy)(MeCN)<sub>2</sub>]<em><sub>n</sub></em> and weakly coordinating anions [Hg{TeFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>]<sup>2–</sup>. In contrast, when a sulfur-based cluster was used in a similar ion-exchange reaction, the resulting cross-linked 1D polymer [{Cu(dpy)(MeCN)}<sub>2</sub>{Hg[SFe<sub>3</sub>(CO)<sub>9</sub>]<sub>2</sub>}]<em><sub>n</sub></em> (<strong>2</strong>) was formed, with the [Hg{SFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] moiety serving as a cross-linker <em>via</em> the Cu–S bond. Further, the three-component mechanochemical reactions of [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em>, chalcogenide clusters [Et<sub>4</sub>N]<sub>2</sub>[Hg{EFe<sub>3</sub>(CO)<sub>9</sub>}<sub>2</sub>] (E = Te, Se), and dpy in a ratio of 2:1:0.5 produced the unique 1D/2D-hybrid cation–anion polymers [{Cu(dpy)(MeCN)<sub>2</sub>}<sub>2</sub>{Cu(dpy)<sub>1.5</sub>(MeCN)}<sub>2</sub>{Hg[EFe<sub>3</sub>(CO)<sub>9</sub>]<sub>2</sub>}<sub>2</sub>]<em><sub>n</sub></em> (E = Te, <strong>3a</strong>; Se, <strong>3b</strong>), respectively. Notably, polymer <strong>3a</strong> could be obtained by the transformation of polymer <strong>1</strong> with dpy <em>via</em> LAG. Detailed single-crystal X-ray analyses revealed extensive weak intermolecular interactions within these polymeric frameworks. Importantly, the cluster-introduced Cu polymers <strong>1, 2, 3a</strong>, and <strong>3b</strong> possessed low optical energy gaps in a range of 1.36–1.63 eV, which was significantly lower than the parent polymer [Cu(dpy)(MeCN)<sub>2</sub>(BF<sub>4</sub>)]<em><sub>n</sub></em> (2.46 eV). Their efficient electron-transport properties were further investigated through density-of-state (DOS) calculations.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1048 ","pages":"Article 124031"},"PeriodicalIF":2.1,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146076036","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 : 2026-01-13DOI: 10.1016/j.jorganchem.2026.124022
Samar Naser Mohammed , Mohammed Faiad Naief , Ahmed Mishaal Mohammed , Ahmed M. Alkaoud , M.H. Eisa , Asmiet Ramizy
Monitoring and controlling hazardous gases is of paramount importance because they cause major public health problems, such as cardiovascular disease, respiratory disease, central nervous system disorders, and other illnesses. The NO2 and NH3 gases are connected to global warming, which in turn affects the environment. Therefore, hazardous emissions should be reduced and eliminated. In this study, AuNPs were synthesized using green chemistry, and then combined with MWCNTs synthesized from agricultural byproducts using an ultrasonic probe approach to develop MWCNT-Au nanocomposite. The nanomaterials were examined using FESEM, TEM, XRD, FTIR, and Raman spectroscopy. The MWCNT-Au gas sensor was tested against NO2 and NH3 gases. The results showed that for both gases, the best resistance response as a function of time was recorded at 25 °C° and a concentration of 100 ppm, while the highest sensitivity values were recorded at 25 °C and 150 °C, respectively. Low response and recovery times were observed for NO2 gas at 150 °C and 200 °C, and for NH3 at 25 °C and 200 °C, respectively. These findings demonstrate that the addition of Au-NPs to the surface of MWCNTs increased their conductivity to both reducing and oxidizing gases. The Langmuir KL and qmax values for NO2 and NH3 were 134.1 mg/g, 0.058 L/mg, 100.7 mg/g, and 0.062 L/mg, respectively. In contrast, the Freundlich Kf and n values for NO2 and NH3 were 16.3, 14.7, 2.1, and 2.3, respectively.
{"title":"High-performance NH₃ and NO₂ gas sensing using synthesized MWCNT-Au nanocomposites","authors":"Samar Naser Mohammed , Mohammed Faiad Naief , Ahmed Mishaal Mohammed , Ahmed M. Alkaoud , M.H. Eisa , Asmiet Ramizy","doi":"10.1016/j.jorganchem.2026.124022","DOIUrl":"10.1016/j.jorganchem.2026.124022","url":null,"abstract":"<div><div>Monitoring and controlling hazardous gases is of paramount importance because they cause major public health problems, such as cardiovascular disease, respiratory disease, central nervous system disorders, and other illnesses. The NO<sub>2</sub> and NH<sub>3</sub> gases are connected to global warming, which in turn affects the environment. Therefore, hazardous emissions should be reduced and eliminated. In this study, AuNPs were synthesized using green chemistry, and then combined with MWCNTs synthesized from agricultural byproducts using an ultrasonic probe approach to develop MWCNT-Au nanocomposite. The nanomaterials were examined using FESEM, TEM, XRD, FTIR, and Raman spectroscopy. The MWCNT-Au gas sensor was tested against NO<sub>2</sub> and NH<sub>3</sub> gases. The results showed that for both gases, the best resistance response as a function of time was recorded at 25 °C° and a concentration of 100 ppm, while the highest sensitivity values were recorded at 25 °C and 150 °C, respectively. Low response and recovery times were observed for NO<sub>2</sub> gas at 150 °C and 200 °C, and for NH<sub>3</sub> at 25 °C and 200 °C, respectively. These findings demonstrate that the addition of Au-NPs to the surface of MWCNTs increased their conductivity to both reducing and oxidizing gases. The Langmuir KL and q<sub>max</sub> values for NO<sub>2</sub> and NH<sub>3</sub> were 134.1 mg/g, 0.058 L/mg, 100.7 mg/g, and 0.062 L/mg, respectively. In contrast, the Freundlich K<sub>f</sub> and n values for NO<sub>2</sub> and NH<sub>3</sub> were 16.3, 14.7, 2.1, and 2.3, respectively.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124022"},"PeriodicalIF":2.1,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975504","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}
In this research, a new and eco-friendly way is described to produce palladium nanoparticles (Pd NPs) that immobilized on graphene oxide using fruit extract of Lycium Barbarum (LB). The GO/Pd NPs was developed by attach the bio-component of the fruit extract of LB and the bio-reduction of palladium ions to palladium nanoparticles over the graphene oxide. Various techniques like TEM, FE-SEM, EDX, ICP-OES, XRD, and elemental mapping were applied to analyze the prepared nanomaterial. As showed by TEM picture, the Pd NPs were evenly sized, round, and about 20 to 30 nanometers wide. The catalytic activity of this easily separable magnetized heterogeneous GO/Pd NPs nanocomposite was successfully examined in the C–N coupling condensation through Buchwald–Hartwig process. Different aryl amines were created by reacting halo arenes (like iodides, bromides, and chlorides) with amines, achieving in good yields. The catalyst can be recycled well even after up to 8 times without drop in its effectiveness.
{"title":"Green decorated palladium nanoparticles over the surface of graphene oxide: An efficient catalyst for Buchwald–Hartwig C–N cross coupling reactions","authors":"Qamar Abuhassan , Supriya S , Subhashree Ray , Renu Sharma , Ahmed Aldulaimi , Omayma Salim Waleed , Rafid Jihad Albadr , Mariem Alwan , Dmitriy Bystrov , Ruslanbek Siddikov , Sardor Sabirov , Aseel Smerat","doi":"10.1016/j.jorganchem.2026.124023","DOIUrl":"10.1016/j.jorganchem.2026.124023","url":null,"abstract":"<div><div>In this research, a new and eco-friendly way is described to produce palladium nanoparticles (Pd NPs) that immobilized on graphene oxide using fruit extract of <em>Lycium Barbarum</em> (LB). The GO/Pd NPs was developed by attach the bio-component of the fruit extract of <em>LB</em> and the bio-reduction of palladium ions to palladium nanoparticles over the graphene oxide. Various techniques like TEM, FE-SEM, EDX, ICP-OES, XRD, and elemental mapping were applied to analyze the prepared nanomaterial. As showed by TEM picture, the Pd NPs were evenly sized, round, and about 20 to 30 nanometers wide. The catalytic activity of this easily separable magnetized heterogeneous GO/Pd NPs nanocomposite was successfully examined in the C–N coupling condensation through Buchwald–Hartwig process. Different aryl amines were created by reacting halo arenes (like iodides, bromides, and chlorides) with amines, achieving in good yields. The catalyst can be recycled well even after up to 8 times without drop in its effectiveness.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1047 ","pages":"Article 124023"},"PeriodicalIF":2.1,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145975505","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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