Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217739
Luca Demonti , Hana Tabikh , Noel Nebra
Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF3) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−Rf bond formations (Rf = F, CF3) are commonly hampered by multiple factors (low nucleophilicity of the F− anion, strong M−CF3 bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−Rf bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF3 couplings taking place from structurally characterized MIVRf species (M = Ni, Pd, Pt; Rf = F, CF3).
The concept of inverted ligand field (ILF) often displayed by some of the ‘formally’ MIVRf species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.
{"title":"Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV)","authors":"Luca Demonti , Hana Tabikh , Noel Nebra","doi":"10.1016/j.ccr.2026.217739","DOIUrl":"10.1016/j.ccr.2026.217739","url":null,"abstract":"<div><div>Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF<sub>3</sub>) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−R<sub>f</sub> bond formations (R<sub>f</sub> = F, CF<sub>3</sub>) are commonly hampered by multiple factors (low nucleophilicity of the F<sup>−</sup> anion, strong M−CF<sub>3</sub> bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−R<sub>f</sub> bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF<sub>3</sub> couplings taking place from structurally characterized M<sup>IV</sup>R<sub>f</sub> species (M = Ni, Pd, Pt; R<sub>f</sub> = F, CF<sub>3</sub>).</div><div>The concept of inverted ligand field (ILF) often displayed by some of the <em>‘formally’</em> M<sup>IV</sup>R<sub>f</sub> species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217739"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217821
Daiane N. Maronde , José E. Rodríguez-Borges , Leandro M.O. Lourenço
Cationic porphyrins (Por) and phthalocyanine (Pc) derivatives are photoactive compounds with strong absorption in the UV–Vis region, making them promising candidates for photodynamic therapy (PDT) against cancer cells. Due to less solubility properties of some compounds in aqueous environments, structural modifications are often required to enhance their amphiphilicity and bioavailability. Introducing positively charged groups, such as e.g., pyridinium or ammonium moieties, into the macrocyclic framework significantly improves water solubility and cellular uptake, optimizing their potential for the PDT approach. This review focuses on the recent advancements in the design and application of cationic Por and Pc dyes for PDT of cancer diseases. Several parameters of the different PDT studies with versatile molecules are analyzed and compared across different structural modifications, light absorption properties (Soret and Q bands), singlet oxygen quantum yield (Ф∆), fluorescence quantum yield (ФF), (photo)stability, and attending to the half-maximal inhibitory concentration (IC50). Additionally, the impact of metal insertion and the nature, number, and position of cationic substituents, peripheral or axial, are discussed in relation to their photodynamic performance. Emphasis is placed on structure activity relationships, the selective accumulation in tumor cells, subcellular localization, and phototoxicity under different light irradiation conditions. This review is distinguished by a critical and comparative assessment of the literature, addressing relevant gaps in previous studies, particularly the insufficient and non-systematic determination of key photophysical parameters. Notwithstanding this standpoint, this review underscores the central role of rational molecular design and structure–activity relationships, contributing significantly to the development of efficient and selective cationic photosensitizers and to the advancement of PDT as a minimally invasive and targeted therapeutic strategy.
{"title":"Advances of light-activated cationic porphyrins and phthalocyanines for cancer photodynamic therapy","authors":"Daiane N. Maronde , José E. Rodríguez-Borges , Leandro M.O. Lourenço","doi":"10.1016/j.ccr.2026.217821","DOIUrl":"10.1016/j.ccr.2026.217821","url":null,"abstract":"<div><div>Cationic porphyrins (Por) and phthalocyanine (Pc) derivatives are photoactive compounds with strong absorption in the UV–Vis region, making them promising candidates for photodynamic therapy (PDT) against cancer cells. Due to less solubility properties of some compounds in aqueous environments, structural modifications are often required to enhance their amphiphilicity and bioavailability. Introducing positively charged groups, such as <em>e.g.</em>, pyridinium or ammonium moieties, into the macrocyclic framework significantly improves water solubility and cellular uptake, optimizing their potential for the PDT approach. This review focuses on the recent advancements in the design and application of cationic Por and Pc dyes for PDT of cancer diseases. Several parameters of the different PDT studies with versatile molecules are analyzed and compared across different structural modifications, light absorption properties (Soret and Q bands), singlet oxygen quantum yield (Ф<sub>∆</sub>), fluorescence quantum yield (Ф<sub>F</sub>), (photo)stability, and attending to the half-maximal inhibitory concentration (IC<sub>50</sub>). Additionally, the impact of metal insertion and the nature, number, and position of cationic substituents, peripheral or axial, are discussed in relation to their photodynamic performance. Emphasis is placed on structure activity relationships, the selective accumulation in tumor cells, subcellular localization, and phototoxicity under different light irradiation conditions. This review is distinguished by a critical and comparative assessment of the literature, addressing relevant gaps in previous studies, particularly the insufficient and non-systematic determination of key photophysical parameters. Notwithstanding this standpoint, this review underscores the central role of rational molecular design and structure–activity relationships, contributing significantly to the development of efficient and selective cationic photosensitizers and to the advancement of PDT as a minimally invasive and targeted therapeutic strategy.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217821"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The unique photophysical properties of cyanine dyes—strong NIR absorption, large molar extinction coefficients, and flexible structural tunability—have positioned them as an important class of photosensitizers for photothermal therapy (PTT) and photodynamic therapy (PDT). However, free cyanine dyes suffer from intrinsic limitations, including poor stability, aggregation-caused quenching (ACQ), low ROS generation, and rapid clearance, which severely restrict their biomedical utility.
Recent advances in molecular self-assembly now offer powerful strategies to overcome these obstacles. Through π–π stacking, hydrophobic interaction, electrostatic association, peptide/protein templating, or metal-ion coordination, cyanine dyes can be organized into highly ordered nanostructures—such as J-aggregates, H-aggregates, nanomicelles, and hybrid nanoassemblies—with precisely tunable morphology and optical behavior. These nanoassemblies restrict conformational freedom, stabilize the excited state, suppress ACQ, and markedly enhance ROS yield and photothermal conversion. In particular, J-aggregates enable red-shifted and sharpened absorption bands, improving tissue penetration and energy utilization for deep-tissue phototherapy.
Beyond enhancing PDT/PTT performance, self-assembled cyanine nanostructures integrate naturally into multifunctional platforms capable of tumor targeting, tumor microenvironment (TME)-responsive activation, multimodal imaging, and combination therapy—such as PTT–PDT synergy, chemo-phototherapy, SDT, or immunotherapy. Despite these promising advances, challenges remain, including controlling assembly stability in vivo, achieving batch-to-batch reproducibility, and predicting biological fate in complex physiological environments.
This review summarizes recent progress in cyanine-dye self-assembly, with emphasis on assembly mechanisms, aggregate-state engineering, structure–property relationships, and strategies for improving PDT/PTT efficacy and combination cancer therapy. We further discuss existing limitations and future opportunities for translating assembled cyanine nanotherapeutics into precision oncology. Together, these insights highlight the power of supramolecular engineering in transforming traditional cyanine dyes into robust, versatile, and clinically meaningful phototheranostic nanoplatforms.
{"title":"Cyanine Nanoassemblies for synergistic cancer therapy: From aggregate-state modulation to Phototheranostic integration","authors":"Di Zhang , Shuheng Qin , Hai Xu , Hui Bian , Yuan-Yuan Zhao , Xiao Cheng , Jinrong Zheng , Xiaojun Peng , Juyoung Yoon","doi":"10.1016/j.ccr.2026.217783","DOIUrl":"10.1016/j.ccr.2026.217783","url":null,"abstract":"<div><div>The unique photophysical properties of cyanine dyes—strong NIR absorption, large molar extinction coefficients, and flexible structural tunability—have positioned them as an important class of photosensitizers for photothermal therapy (PTT) and photodynamic therapy (PDT). However, free cyanine dyes suffer from intrinsic limitations, including poor stability, aggregation-caused quenching (ACQ), low ROS generation, and rapid clearance, which severely restrict their biomedical utility.</div><div>Recent advances in molecular self-assembly now offer powerful strategies to overcome these obstacles. Through π–π stacking, hydrophobic interaction, electrostatic association, peptide/protein templating, or metal-ion coordination, cyanine dyes can be organized into highly ordered nanostructures—such as J-aggregates, H-aggregates, nanomicelles, and hybrid nanoassemblies—with precisely tunable morphology and optical behavior. These nanoassemblies restrict conformational freedom, stabilize the excited state, suppress ACQ, and markedly enhance ROS yield and photothermal conversion. In particular, J-aggregates enable red-shifted and sharpened absorption bands, improving tissue penetration and energy utilization for deep-tissue phototherapy.</div><div>Beyond enhancing PDT/PTT performance, self-assembled cyanine nanostructures integrate naturally into multifunctional platforms capable of tumor targeting, tumor microenvironment (TME)-responsive activation, multimodal imaging, and combination therapy—such as PTT–PDT synergy, chemo-phototherapy, SDT, or immunotherapy. Despite these promising advances, challenges remain, including controlling assembly stability in vivo, achieving batch-to-batch reproducibility, and predicting biological fate in complex physiological environments.</div><div>This review summarizes recent progress in cyanine-dye self-assembly, with emphasis on assembly mechanisms, aggregate-state engineering, structure–property relationships, and strategies for improving PDT/PTT efficacy and combination cancer therapy. We further discuss existing limitations and future opportunities for translating assembled cyanine nanotherapeutics into precision oncology. Together, these insights highlight the power of supramolecular engineering in transforming traditional cyanine dyes into robust, versatile, and clinically meaningful phototheranostic nanoplatforms.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217783"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217819
Yusu Li , Xinyue Zhao , Jin-ao Duan, Ping Xiao
The growing global antimicrobial resistance crisis and limitations of conventional cancer therapies call for innovative biomedical strategies. Peptide-metal chelates are promising multifunctional biomaterials that leverage peptide-metal ion synergy to overcome traditional therapeutic bottlenecks, with core value in building integrated platforms for programmable targeted delivery, spatiotemporal smart responsiveness and intrinsic theranostic synergy. Research in this field has evolved from basic molecular discovery to systematic rational design and now clinical smart applications. This review presents a novel research and development roadmap for peptide-metal chelates, elaborating their design principles, structure-function mechanisms and latest biomedical advances. It highlights their unique “Trojan horse” strategy for antibacterial resistance and precise tumor targeting via the EPR effect and tumor microenvironmental triggers such as pH and enzymes. It details their applications in intelligent drug delivery, high-efficacy antimicrobial therapy, precision anticancer treatment, and theranostic platforms integrating imaging and therapy. Addressing gaps in existing fragmented summaries, including the lack of systematic design-synthesis-application integration and insufficient basic-clinical translation analysis, the review also notes unresolved challenges in long-term in vivo safety, bioavailability optimization and GMP-compliant large-scale production. Finally, it prospects core directions like AI-assisted rational molecular design, advanced multi-stimuli responsive materials and multimodal theranostic integration, which are expected to accelerate the clinical translation of peptide-metal chelates and offer innovative solutions for drug-resistant infections and refractory cancers.
{"title":"Design mechanisms and biomedical applications of peptide-metal chelates in antimicrobial therapy, tumor theranostics, and integrated diagnosis-treatment systems","authors":"Yusu Li , Xinyue Zhao , Jin-ao Duan, Ping Xiao","doi":"10.1016/j.ccr.2026.217819","DOIUrl":"10.1016/j.ccr.2026.217819","url":null,"abstract":"<div><div>The growing global antimicrobial resistance crisis and limitations of conventional cancer therapies call for innovative biomedical strategies. Peptide-metal chelates are promising multifunctional biomaterials that leverage peptide-metal ion synergy to overcome traditional therapeutic bottlenecks, with core value in building integrated platforms for programmable targeted delivery, spatiotemporal smart responsiveness and intrinsic theranostic synergy. Research in this field has evolved from basic molecular discovery to systematic rational design and now clinical smart applications. This review presents a novel research and development roadmap for peptide-metal chelates, elaborating their design principles, structure-function mechanisms and latest biomedical advances. It highlights their unique “Trojan horse” strategy for antibacterial resistance and precise tumor targeting <em>via</em> the EPR effect and tumor microenvironmental triggers such as pH and enzymes. It details their applications in intelligent drug delivery, high-efficacy antimicrobial therapy, precision anticancer treatment, and theranostic platforms integrating imaging and therapy. Addressing gaps in existing fragmented summaries, including the lack of systematic design-synthesis-application integration and insufficient basic-clinical translation analysis, the review also notes unresolved challenges in long-term <em>in vivo</em> safety, bioavailability optimization and GMP-compliant large-scale production. Finally, it prospects core directions like AI-assisted rational molecular design, advanced multi-stimuli responsive materials and multimodal theranostic integration, which are expected to accelerate the clinical translation of peptide-metal chelates and offer innovative solutions for drug-resistant infections and refractory cancers.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217819"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217809
K. Keerthi , E.A. Lohith , Sowjanya Vallem , K. Praveena , Dimpul Konwar , Kasibhatta Sivakumar , Rajenahally V. Jagadeesh , N.V.V. Jyothi , Aristides Bakandritsos , Sada Venkateswarlu , Minyoung Yoon , Radek Zboril
Organic pollutants, including plastics, pharmaceuticals, aromatic compounds, pesticides, and industrial solvents, pose a serious threat to soil quality, aquatic ecosystems, and human health. Single-atom-coordinated MXenes (SAs@MXenes) have emerged as promising platforms for detoxifying organic pollutants because of their tunable surface chemistry, high catalytic activity, and atomic-level precision. Anchoring isolated metal atoms on the MXene surface maximizes atom utilization and modulates the electronic structure, thereby improving charge separation, adsorption affinity, and redox reactivity. However, comprehensive reviews of this emerging class of SAs@MXenes catalysts for organic pollutant detoxification remain limited. This review summarizes diverse synthesis strategies for achieving stable single-atom dispersion, including defect engineering to anchor single atoms at vacancy sites, heteroatom coordination chemistry, axial coordination, the modulation of local electronic structure through ligand control, and UV-mediated synthesis that enables photochemical precision in atom placement. In addition, advanced characterization techniques are used to confirm atomic dispersion, oxidation states, and structural evolution, while electron paramagnetic resonance (EPR) spectroscopy provides insight into the reactive intermediates responsible for detoxification. Furthermore, SAs@MXenes function as both efficient catalysts and a robust adsorbents for the degradation and capture of organic contaminants. Computational approaches, including density functional theory (DFT), machine learning (ML), and molecular dynamics (MD) simulations, are emphasized to elucidate catalytic mechanisms, accelerate catalytic design, and clarify molecular-level interactions. Collectively, these strategies support the rational development of single-atom–coordinated MXenes for sustainable environmental detoxification, and their future perspectives are also presented.
{"title":"Single-atom coordinated MXenes for organic pollutant detoxification: Mechanistic insights, challenges, and future directions","authors":"K. Keerthi , E.A. Lohith , Sowjanya Vallem , K. Praveena , Dimpul Konwar , Kasibhatta Sivakumar , Rajenahally V. Jagadeesh , N.V.V. Jyothi , Aristides Bakandritsos , Sada Venkateswarlu , Minyoung Yoon , Radek Zboril","doi":"10.1016/j.ccr.2026.217809","DOIUrl":"10.1016/j.ccr.2026.217809","url":null,"abstract":"<div><div>Organic pollutants, including plastics, pharmaceuticals, aromatic compounds, pesticides, and industrial solvents, pose a serious threat to soil quality, aquatic ecosystems, and human health. Single-atom-coordinated MXenes (SAs@MXenes) have emerged as promising platforms for detoxifying organic pollutants because of their tunable surface chemistry, high catalytic activity, and atomic-level precision. Anchoring isolated metal atoms on the MXene surface maximizes atom utilization and modulates the electronic structure, thereby improving charge separation, adsorption affinity, and redox reactivity. However, comprehensive reviews of this emerging class of SAs@MXenes catalysts for organic pollutant detoxification remain limited<strong>.</strong> This review summarizes diverse synthesis strategies for achieving stable single-atom dispersion, including defect engineering to anchor single atoms at vacancy sites, heteroatom coordination chemistry, axial coordination, the modulation of local electronic structure through ligand control, and UV-mediated synthesis that enables photochemical precision in atom placement. In addition, advanced characterization techniques are used to confirm atomic dispersion, oxidation states, and structural evolution, while electron paramagnetic resonance (EPR) spectroscopy provides insight into the reactive intermediates responsible for detoxification. Furthermore, SAs@MXenes function as both efficient catalysts and a robust adsorbents for the degradation and capture of organic contaminants. Computational approaches, including density functional theory (DFT), machine learning (ML), and molecular dynamics (MD) simulations, are emphasized to elucidate catalytic mechanisms, accelerate catalytic design, and clarify molecular-level interactions. Collectively, these strategies support the rational development of single-atom–coordinated MXenes for sustainable environmental detoxification, and their future perspectives are also presented.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217809"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217808
Parinaz Mofazali , Minoosh Lalinia , Jeffrey D. Gross , Ali Samadi
The review examines molecularly imprinted polymers (MIPs) technology and its potential applications to present current scientific progress in the field. It highlights that MIPs production at an industrial scale faces difficulties because different types of intermolecular interactions and polymerization conditions and material performance create complex synthesis challenges. Emphasis is placed on the versatility of MIPs in environmental monitoring, the food industry, extraction, sensors, drug delivery, and biomedicine, with the discussion on the integration of MIPs pointing out the possibilities for enhancing accuracy and reliability. Furthermore, combining MIPs with analytical and computational methods creates new opportunities for qualitative and quantitative evaluation. In this light, the application of artificial intelligence (AI) to improve MIP performance, expedite polymerization procedures, and forecast ideal monomer-template interactions is expanding. This manuscript offers a fresh viewpoint using combined MIP applications in biosensing, drug delivery, environmental treatment, food safety, and catalysis with AI-driven strategies. It also aims to establish a framework for the future development of the next generation of smart and sustainable technologies.
{"title":"Molecularly imprinted polymers: applications, computational approaches, and the transformative role of artificial intelligence","authors":"Parinaz Mofazali , Minoosh Lalinia , Jeffrey D. Gross , Ali Samadi","doi":"10.1016/j.ccr.2026.217808","DOIUrl":"10.1016/j.ccr.2026.217808","url":null,"abstract":"<div><div>The review examines molecularly imprinted polymers (MIPs) technology and its potential applications to present current scientific progress in the field. It highlights that MIPs production at an industrial scale faces difficulties because different types of intermolecular interactions and polymerization conditions and material performance create complex synthesis challenges. Emphasis is placed on the versatility of MIPs in environmental monitoring, the food industry, extraction, sensors, drug delivery, and biomedicine, with the discussion on the integration of MIPs pointing out the possibilities for enhancing accuracy and reliability. Furthermore, combining MIPs with analytical and computational methods creates new opportunities for qualitative and quantitative evaluation. In this light, the application of artificial intelligence (AI) to improve MIP performance, expedite polymerization procedures, and forecast ideal monomer-template interactions is expanding. This manuscript offers a fresh viewpoint using combined MIP applications in biosensing, drug delivery, environmental treatment, food safety, and catalysis with AI-driven strategies. It also aims to establish a framework for the future development of the next generation of smart and sustainable technologies.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217808"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388424","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-07-15Epub Date: 2026-03-11DOI: 10.1016/j.ccr.2026.217797
Rui Wang , Xingqiao Deng , Bo Hu , Mule Vijayalakshmi , Hui Tang , Liang He , Xuemeng Liu , Ch. Venkata Reddy , Kakarla Raghava Reddy , Jaesool Shim , Tejraj M. Aminabhavi
Transition metal sulfides (TMSs) are compounds composed of sulfur anions and one or more transition metal cations. They are characterized by having multiple crystal phases and electronic structures, including metallic, semiconducting, and insulating states. These tunable and controllable polycrystalline phases and electronic structures endow TMSs with unique physical and electrochemical properties, making them highly promising for energy-sector applications. Even though significant progress has been made in this field, most studies remain confined to idealized systems with only half-reactions, lacking a systematic understanding of the relationship between the intrinsic properties of materials and catalytic mechanisms, and ignoring the essential differences between half-reactions and complete reaction systems. To fully exploit the potential advantages of TMSs, it is necessary to clarify their mechanism of action in different catalytic processes systematically to establish a clear correlation between structural characteristics, intrinsic properties, and catalytic activity to gradually shift from qualitative studies focusing on single half-reactions to full-reaction application research in order to promote their practical development at the industrial and commercial scales. This review systematically summarizes recent advances in TMS-based electrocatalysts, covering preparation methods, structural features, and modification strategies, to establish a framework for rational structural design. Then elucidates the key electrocatalytic mechanisms that correlate catalytic performance with structural characteristics, thereby guiding the development of efficient catalysts. Finally, the review critically evaluates the application of TMS-based electrocatalysts in energy conversion devices beyond isolated half-reaction studies, identifies current challenges in practical implementation and commercialization, and outlines potential directions for future development.
{"title":"Advances in transition metal sulfides: Synthesis, properties, and modification strategies for electrocatalysis and energy conversion applications","authors":"Rui Wang , Xingqiao Deng , Bo Hu , Mule Vijayalakshmi , Hui Tang , Liang He , Xuemeng Liu , Ch. Venkata Reddy , Kakarla Raghava Reddy , Jaesool Shim , Tejraj M. Aminabhavi","doi":"10.1016/j.ccr.2026.217797","DOIUrl":"10.1016/j.ccr.2026.217797","url":null,"abstract":"<div><div>Transition metal sulfides (TMSs) are compounds composed of sulfur anions and one or more transition metal cations. They are characterized by having multiple crystal phases and electronic structures, including metallic, semiconducting, and insulating states. These tunable and controllable polycrystalline phases and electronic structures endow TMSs with unique physical and electrochemical properties, making them highly promising for energy-sector applications. Even though significant progress has been made in this field, most studies remain confined to idealized systems with only half-reactions, lacking a systematic understanding of the relationship between the intrinsic properties of materials and catalytic mechanisms, and ignoring the essential differences between half-reactions and complete reaction systems. To fully exploit the potential advantages of TMSs, it is necessary to clarify their mechanism of action in different catalytic processes systematically to establish a clear correlation between structural characteristics, intrinsic properties, and catalytic activity to gradually shift from qualitative studies focusing on single half-reactions to full-reaction application research in order to promote their practical development at the industrial and commercial scales. This review systematically summarizes recent advances in TMS-based electrocatalysts, covering preparation methods, structural features, and modification strategies, to establish a framework for rational structural design. Then elucidates the key electrocatalytic mechanisms that correlate catalytic performance with structural characteristics, thereby guiding the development of efficient catalysts. Finally, the review critically evaluates the application of TMS-based electrocatalysts in energy conversion devices beyond isolated half-reaction studies, identifies current challenges in practical implementation and commercialization, and outlines potential directions for future development.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217797"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388425","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stimuli-responsive inorganic–organic frameworks (IOFs) are a class of functional materials, can controllably respond to one or more external stimuli. Among various organic linkers employed in IOF design, naphthalene diimides (NDIs) are of great interest because of their rigid and planar structure, electron-deficient character, and tunable electronic properties. The NDI derivatives are suitable for applications in optoelectronics, photochromic displays, electrochromic devices, chemical sensing, and rewritable media. In spite of the progress made recently in the synthesis of NDI-based ligands, NDI derivatives remain underexplored in crystalline hybrid materials (CHNs) due to synthetic challenges. This review comprehensively summarizes advances in NDI-CHNs, with a focus on highlighting structure–function relationships, as well as emerging functionalities, thereby offering theoretical insight and practical guidance for future research.
{"title":"Progress of naphthalene diimides crystalline hybrid networks in design and applications","authors":"Zi-Xin You , Ting Zhang , Qing-Lin Guan , Chao Zhang , Ming-Dong Zhou , Xing-Jing Zhang , Yong-Heng Xing","doi":"10.1016/j.ccr.2026.217696","DOIUrl":"10.1016/j.ccr.2026.217696","url":null,"abstract":"<div><div>Stimuli-responsive inorganic–organic frameworks (IOFs) are a class of functional materials, can controllably respond to one or more external stimuli. Among various organic linkers employed in IOF design, naphthalene diimides (NDIs) are of great interest because of their rigid and planar structure, electron-deficient character, and tunable electronic properties. The NDI derivatives are suitable for applications in optoelectronics, photochromic displays, electrochromic devices, chemical sensing, and rewritable media. In spite of the progress made recently in the synthesis of NDI-based ligands, NDI derivatives remain underexplored in crystalline hybrid materials (CHNs) due to synthetic challenges. This review comprehensively summarizes advances in NDI-CHNs, with a focus on highlighting structure–function relationships, as well as emerging functionalities, thereby offering theoretical insight and practical guidance for future research.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"556 ","pages":"Article 217696"},"PeriodicalIF":23.5,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146160635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-02-05DOI: 10.1016/j.ccr.2026.217632
Yihong Mo , Yulu Chen , Haifu Zhang , Wenhai Feng , Fengxue Duan , Huhai Chen , Zhuoxi Su , Xiaofei Chen , Yifa Chen , Ya-Qian Lan
Ether‑oxygen based covalent organic frameworks (EO-COFs) represent an emerging class of porous crystalline materials that uniquely integrate the dynamic flexibility of ether‑oxygen (EO) bonds with the structural order of covalent organic frameworks (COFs). Compared to other COFs, EO-COFs exhibit remarkable structural adaptability, excellent chemical and thermal stability, and versatile post-modification compatibility, owing to tunable conformation and robust electronic nature of the C-O-C linkages. Since their first report in 2015, EO-COFs have demonstrated considerable application potential in multiple fields, including adsorption/separation, catalysis, chemical sensing, and energy storage, etc. These materials not only inherit the flexibility of EO polymers but also significantly enhance the porosity and crystallinity of COFs, thereby expanding their functionality and application scope. However, critical knowledge gaps persist in EO-COFs research, particularly in establishing quantitative structure-performance correlations, innovating low-cost synthetic pathways, and tailoring materials for advanced application fields. Therefore, this review will systematically summarize the preparation methods, properties, and application prospects of EO-COFs and discuss the development opportunities and challenges. We anticipate this review will stimulate more perspectives and new ideas for developing advanced functionalities and expanding regimes of EO-COFs.
{"title":"Ether-oxygen based covalent organic frameworks: a new cognitive guide","authors":"Yihong Mo , Yulu Chen , Haifu Zhang , Wenhai Feng , Fengxue Duan , Huhai Chen , Zhuoxi Su , Xiaofei Chen , Yifa Chen , Ya-Qian Lan","doi":"10.1016/j.ccr.2026.217632","DOIUrl":"10.1016/j.ccr.2026.217632","url":null,"abstract":"<div><div>Ether‑oxygen based covalent organic frameworks (EO-COFs) represent an emerging class of porous crystalline materials that uniquely integrate the dynamic flexibility of ether‑oxygen (EO) bonds with the structural order of covalent organic frameworks (COFs). Compared to other COFs, EO-COFs exhibit remarkable structural adaptability, excellent chemical and thermal stability, and versatile post-modification compatibility, owing to tunable conformation and robust electronic nature of the C-O-C linkages. Since their first report in 2015, EO-COFs have demonstrated considerable application potential in multiple fields, including adsorption/separation, catalysis, chemical sensing, and energy storage, etc. These materials not only inherit the flexibility of EO polymers but also significantly enhance the porosity and crystallinity of COFs, thereby expanding their functionality and application scope. However, critical knowledge gaps persist in EO-COFs research, particularly in establishing quantitative structure-performance correlations, innovating low-cost synthetic pathways, and tailoring materials for advanced application fields. Therefore, this review will systematically summarize the preparation methods, properties, and application prospects of EO-COFs and discuss the development opportunities and challenges. We anticipate this review will stimulate more perspectives and new ideas for developing advanced functionalities and expanding regimes of EO-COFs.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"556 ","pages":"Article 217632"},"PeriodicalIF":23.5,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146115953","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-02-05DOI: 10.1016/j.ccr.2026.217666
Sadia Muzammal , Awais Ahmad , Tahir Rasheed , Muhammad Usman , Abdullah Aitani , Franics Verpoot , Abid Ali , Arfaa Sajid , N.A.S. Amin
The global shift towards renewable energy sources necessitates the progress of safe, sustainable, and high-performance energy storage technologies. Traditional metal-ion batteries, although dominant in current applications, face significant limitations, including resource scarcity, high costs, environmental impact, and safety risks. In response, non-metal ion batteries (NMIBs) have emerged as a promising class of energy storage systems that utilize non-metallic charge carriers, including protons (H+), hydronium (H3O+), ammonium (NH4+), halide ions (Cl−, Br−), and organic ions, as alternatives to metal ions. These systems offer numerous advantages, including fast ion diffusion, biocompatibility, design flexibility, and a reduced ecological footprint. This review presents a comprehensive overview of NMIBs, detailing their fundamental working principles, classification, electrode and electrolyte materials, electrochemical performance, and the distinct mechanisms underlying their operation. Special emphasis is placed on recent advances in advanced functional materials, such as MXenes, MOFs, and redox-active organics, that enhance ionic conductivity and cycle stability. The review also outlines current challenges and research gaps while providing strategic insights into the future direction of this emerging field. By highlighting the potential of NMIBs as viable successors to traditional technologies, this work contributes to the broader vision of achieving sustainable and scalable energy storage solutions.
{"title":"Non-metallic ion batteries beyond convention: fundamentals, material innovations, and pathways to sustainable energy storage","authors":"Sadia Muzammal , Awais Ahmad , Tahir Rasheed , Muhammad Usman , Abdullah Aitani , Franics Verpoot , Abid Ali , Arfaa Sajid , N.A.S. Amin","doi":"10.1016/j.ccr.2026.217666","DOIUrl":"10.1016/j.ccr.2026.217666","url":null,"abstract":"<div><div>The global shift towards renewable energy sources necessitates the progress of safe, sustainable, and high-performance energy storage technologies. Traditional metal-ion batteries, although dominant in current applications, face significant limitations, including resource scarcity, high costs, environmental impact, and safety risks. In response, non-metal ion batteries (NMIBs) have emerged as a promising class of energy storage systems that utilize non-metallic charge carriers, including protons (H<sup>+</sup>), hydronium (H<sub>3</sub>O<sup>+</sup>), ammonium (NH<sub>4</sub><sup>+</sup>), halide ions (Cl<sup>−</sup>, Br<sup>−</sup>), and organic ions, as alternatives to metal ions. These systems offer numerous advantages, including fast ion diffusion, biocompatibility, design flexibility, and a reduced ecological footprint. This review presents a comprehensive overview of NMIBs, detailing their fundamental working principles, classification, electrode and electrolyte materials, electrochemical performance, and the distinct mechanisms underlying their operation. Special emphasis is placed on recent advances in advanced functional materials, such as MXenes, MOFs, and redox-active organics, that enhance ionic conductivity and cycle stability. The review also outlines current challenges and research gaps while providing strategic insights into the future direction of this emerging field. By highlighting the potential of NMIBs as viable successors to traditional technologies, this work contributes to the broader vision of achieving sustainable and scalable energy storage solutions.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"556 ","pages":"Article 217666"},"PeriodicalIF":23.5,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135113","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}