Feifei Liu, Yue Shi, Yujia Guan, Jiaxuan Zhou, Hongdong Li, Jingqi Chi, Jianping Lai, Lei Wang
In recent years, in situ generated integrated metal-based composite materials have garnered widespread attention in the field of electrocatalysis due to their advantages such as high reactivity, long lifespan, and rapid electron transfer rates. By employing different synthesis strategies to regulate their structure and composition, the reactivity and selectivity of these materials can be precisely tuned, thereby laying a foundation for designing efficient catalysts tailored for specific reactions. This article systematically reviews the construction methods, regulation strategies, and applications of in situ generated integrated metal-based composite nanocatalysts in various reactions. It also explores the potential of emerging technologies and innovative approaches in material design, performance optimization, and electronic structure modulation. Finally, the main challenges currently facing this field are discussed, along with potential future development directions. Through this comprehensive overview, the aim is to provide valuable insights for advancing the further development of in situ generated integrated metal-based composite nanocatalysts and promoting their widespread deployment in catalytic applications.
{"title":"In situ integrated construction of electrocatalysts: from microscopic control to macroscopic performance","authors":"Feifei Liu, Yue Shi, Yujia Guan, Jiaxuan Zhou, Hongdong Li, Jingqi Chi, Jianping Lai, Lei Wang","doi":"10.1039/d5qi02233a","DOIUrl":"https://doi.org/10.1039/d5qi02233a","url":null,"abstract":"In recent years, <em>in situ</em> generated integrated metal-based composite materials have garnered widespread attention in the field of electrocatalysis due to their advantages such as high reactivity, long lifespan, and rapid electron transfer rates. By employing different synthesis strategies to regulate their structure and composition, the reactivity and selectivity of these materials can be precisely tuned, thereby laying a foundation for designing efficient catalysts tailored for specific reactions. This article systematically reviews the construction methods, regulation strategies, and applications of <em>in situ</em> generated integrated metal-based composite nanocatalysts in various reactions. It also explores the potential of emerging technologies and innovative approaches in material design, performance optimization, and electronic structure modulation. Finally, the main challenges currently facing this field are discussed, along with potential future development directions. Through this comprehensive overview, the aim is to provide valuable insights for advancing the further development of <em>in situ</em> generated integrated metal-based composite nanocatalysts and promoting their widespread deployment in catalytic applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993201","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}
Jessica Toigo, Ka-Ming Tong, Saeid Kamal, Charles J. Walsby, Brian O. Patrick, Michael O. Wolf
The ultrafast decay inherent to metal complexes with a 3d6 configuration limits their application as photosensitizers. Despite recent advances in improving the photophysical properties of these complexes, existing ligand designs restrict further modification and are often synthetically challenging. Here, we show how sulfur-bridged ligands can be used to tune the structural and photophysical properties in Co(III) photosensitizers. Two complexes, CoS ([Co(PTZIm2)2]PF6) and CoSO2 ([Co(PTZO2Im2)2]PF6), adopt facial geometries due to a less rigid ligand backbone compared to other pincer-type ligands. The lowest-lying absorption bands of both CoS and CoSO2 display metal/ligand-to-ligand charge-transfer (M + L)LCT character with different contributions from the sulfur-bridged ligand. TD-DFT analysis indicates that CoSO2 has a lower contribution from the phenothiazine moiety to the band at 400 nm. The sulfur oxidation state also affects the electronic density at the metal center, with CoS showing a lower MIV/III oxidation potential. Transient absorption experiments reveal that fast non-radiative decay channels are facilitated in CoS. However, a photoactive long-lived component (8.0 ns) is also observed. Oxidation of phenothiazine extends the lifetimes of short-lived components in CoSO2, where both electronic and structural effects may be playing a role. These findings demonstrate that the photophysical properties of Co(III) complexes can be modulated by variation of the sulfur oxidation state to achieve different photophysical properties of the complexes.
{"title":"Photophysical properties of Co(III) photosensitizers with phenothiazine-based ligands","authors":"Jessica Toigo, Ka-Ming Tong, Saeid Kamal, Charles J. Walsby, Brian O. Patrick, Michael O. Wolf","doi":"10.1039/d5qi02362a","DOIUrl":"https://doi.org/10.1039/d5qi02362a","url":null,"abstract":"The ultrafast decay inherent to metal complexes with a 3d<small><sup>6</sup></small> configuration limits their application as photosensitizers. Despite recent advances in improving the photophysical properties of these complexes, existing ligand designs restrict further modification and are often synthetically challenging. Here, we show how sulfur-bridged ligands can be used to tune the structural and photophysical properties in Co(<small>III</small>) photosensitizers. Two complexes, <strong>CoS</strong> ([Co(PTZIm<small><sub>2</sub></small>)<small><sub>2</sub></small>]PF<small><sub>6</sub></small>) and <strong>CoSO<small><sub>2</sub></small></strong> ([Co(PTZO<small><sub>2</sub></small>Im<small><sub>2</sub></small>)<small><sub>2</sub></small>]PF<small><sub>6</sub></small>), adopt facial geometries due to a less rigid ligand backbone compared to other pincer-type ligands. The lowest-lying absorption bands of both <strong>CoS</strong> and <strong>CoSO<small><sub>2</sub></small></strong> display metal/ligand-to-ligand charge-transfer (M + L)LCT character with different contributions from the sulfur-bridged ligand. TD-DFT analysis indicates that <strong>CoSO<small><sub>2</sub></small></strong> has a lower contribution from the phenothiazine moiety to the band at 400 nm. The sulfur oxidation state also affects the electronic density at the metal center, with <strong>CoS</strong> showing a lower M<small><sup>IV/III</sup></small> oxidation potential. Transient absorption experiments reveal that fast non-radiative decay channels are facilitated in <strong>CoS</strong>. However, a photoactive long-lived component (8.0 ns) is also observed. Oxidation of phenothiazine extends the lifetimes of short-lived components in <strong>CoSO<small><sub>2</sub></small></strong>, where both electronic and structural effects may be playing a role. These findings demonstrate that the photophysical properties of Co(<small>III</small>) complexes can be modulated by variation of the sulfur oxidation state to achieve different photophysical properties of the complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"58 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993174","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}
Daniel Franz, Thomas R Frost, Sebastian Stigler, Shigeyoshi Inoue
The Main Group Lewis Superacid complexes (pinF)2Si∙MeCN (1∙MeCN) and (pinF)2Ge∙MeCN (2∙MeCN) were successfully applied as promotors in the catalytic reduction of phosphine oxides (e.g. Me3PO, Bu3PO, Ph3PO), sulfoxide (i.e. Me2SO), and amide (i.e. Me2NCHO) to furnish the respective phosphines, dimethyl sulfide, and trimethylamine using silanes (e.g. PhSiH3, (EtO)3SiH) as hydrogen sources (pinF = perfluoropinacolato). These substrates mark difficult to reduce representatives for oxo compounds in comparison to, for example, the ketones or aldehydes often targeted in such type of catalytic reductions. As benchmark promotors, we also studied B(C6F5)3 and HNTf2 as reference (soft) Lewis Superacid and Brønsted Superacid, respectively (Tf = SO2CF3). Under consideration of the investigated combinations of (pre)catalyst, substrate and reducing agent the silicon complex 1∙MeCN turned out as the most versatile system being the most potent (DMSO) or just slightly outperformed (R3PO, DMF) promotor. Moreover, the hitherto undescribed Lewis acid base adducts 1∙Me2NCHO and 2∙Me2SO were synthesized, isolated and structurally investigated by NMR spectroscopy and Single Crystal XRD Analysis
{"title":"Lewis Superacids for Catalytic Reductions of Stronger Element Oxygen Double Bonds with Hydrosilanes","authors":"Daniel Franz, Thomas R Frost, Sebastian Stigler, Shigeyoshi Inoue","doi":"10.1039/d5qi02493e","DOIUrl":"https://doi.org/10.1039/d5qi02493e","url":null,"abstract":"The Main Group Lewis Superacid complexes (pinF)2Si∙MeCN (1∙MeCN) and (pinF)2Ge∙MeCN (2∙MeCN) were successfully applied as promotors in the catalytic reduction of phosphine oxides (e.g. Me3PO, Bu3PO, Ph3PO), sulfoxide (i.e. Me2SO), and amide (i.e. Me2NCHO) to furnish the respective phosphines, dimethyl sulfide, and trimethylamine using silanes (e.g. PhSiH3, (EtO)3SiH) as hydrogen sources (pinF = perfluoropinacolato). These substrates mark difficult to reduce representatives for oxo compounds in comparison to, for example, the ketones or aldehydes often targeted in such type of catalytic reductions. As benchmark promotors, we also studied B(C6F5)3 and HNTf2 as reference (soft) Lewis Superacid and Brønsted Superacid, respectively (Tf = SO2CF3). Under consideration of the investigated combinations of (pre)catalyst, substrate and reducing agent the silicon complex 1∙MeCN turned out as the most versatile system being the most potent (DMSO) or just slightly outperformed (R3PO, DMF) promotor. Moreover, the hitherto undescribed Lewis acid base adducts 1∙Me2NCHO and 2∙Me2SO were synthesized, isolated and structurally investigated by NMR spectroscopy and Single Crystal XRD Analysis","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993200","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}
Haruka Koshino, Masato Shimada, Hiroki Yamada, Kanta Takiishi, Miki Inada, Zi Lang Goo, Kunihisa Sugimoto, Tomoyuki Mochida
Solvent-free strategies for constructing coordination assemblies are desirable but remain challenging. We investigated the photochemical reactivity of ionic liquids (ILs) composed of a sandwich-type Ru complex bearing a dialkylaniline ligand, [CpRu(PhNMeC6H13)]+, and cyanoborate anions (B(CN)4–, BEt2(CN)2–, BF2(CN)2–). Upon UV irradiation, these ILs underwent ligand dissociation and formed polynuclear Ru complexes: the B(CN)4 salt yielded a cubane-type tetranuclear complex, whereas the BEt2(CN)2 and BF2(CN)2 salts produced dinuclear species. These structural transformations resulted in a reduction of ionic conductivity by more than one order of magnitude, with full reversibility observed for the B(CN)4 salt and near-complete reversibility for the others, which exhibited minor thermal decomposition. In contrast, the IL incorporating a cyanoalkyl-substituted arene ligand, [CpRu(PhC4H8CN)]BF2(CN)2, formed an amorphous, viscoelastomeric coordination polymer and did not exhibit thermal reversibility. This study presents a solvent-free approach for the construction of reversible, photoresponsive ionic assemblies with tunable ionic conductivity.
{"title":"Photoinduced Reversible Assembly of Polynuclear Complexes from Ru-Containing Ionic Liquids with Accompanying Ionic Conductivity Modulations","authors":"Haruka Koshino, Masato Shimada, Hiroki Yamada, Kanta Takiishi, Miki Inada, Zi Lang Goo, Kunihisa Sugimoto, Tomoyuki Mochida","doi":"10.1039/d5qi02318a","DOIUrl":"https://doi.org/10.1039/d5qi02318a","url":null,"abstract":"Solvent-free strategies for constructing coordination assemblies are desirable but remain challenging. We investigated the photochemical reactivity of ionic liquids (ILs) composed of a sandwich-type Ru complex bearing a dialkylaniline ligand, [CpRu(PhNMeC<small><sub>6</sub></small>H<small><sub>13</sub></small>)]<small><sup>+</sup></small>, and cyanoborate anions (B(CN)<small><sub>4</sub></small><small><sup>–</sup></small>, BEt<small><sub>2</sub></small>(CN)<small><sub>2</sub></small><small><sup>–</sup></small>, BF<small><sub>2</sub></small>(CN)<small><sub>2</sub></small><small><sup>–</sup></small>). Upon UV irradiation, these ILs underwent ligand dissociation and formed polynuclear Ru complexes: the B(CN)<small><sub>4</sub></small> salt yielded a cubane-type tetranuclear complex, whereas the BEt<small><sub>2</sub></small>(CN)<small><sub>2</sub></small> and BF<small><sub>2</sub></small>(CN)<small><sub>2</sub></small> salts produced dinuclear species. These structural transformations resulted in a reduction of ionic conductivity by more than one order of magnitude, with full reversibility observed for the B(CN)<small><sub>4</sub></small> salt and near-complete reversibility for the others, which exhibited minor thermal decomposition. In contrast, the IL incorporating a cyanoalkyl-substituted arene ligand, [CpRu(PhC<small><sub>4</sub></small>H<small><sub>8</sub></small>CN)]BF<small><sub>2</sub></small>(CN)<small><sub>2</sub></small>, formed an amorphous, viscoelastomeric coordination polymer and did not exhibit thermal reversibility. This study presents a solvent-free approach for the construction of reversible, photoresponsive ionic assemblies with tunable ionic conductivity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"266 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968974","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}
We report a selective metallation strategy that enables the controlled incorporation of one or two distinct metal ions within a chiral and symmetric tris(2-pyridylmethyl)amine (TPMA)-based molecular cage. Unlike typical homoditopic ligands, which often lead to scrambling and statistical mixtures, our approach affords well-defined mononuclear (CoH4) and heterodinuclear (CoZn, CoCu) complexes in a straightforward and reproducible manner. This represents a rare example of heterometallic cage complexes from a symmetric scaffold, where the stepwise addition of metal ions affords well-defined mono- and dinuclear species. To illustrate the functional relevance of this strategy, we evaluated the photocatalytic hydrogen evolution activity of the different mono- and dinuclear complexes. The results reveal that the mononuclear CoH4 cage displays the highest performance, which we propose to arise from second-sphere proton transfer facilitated by the non-coordinated TPMA unit. Complementary DFT calculations support this mechanistic hypothesis. Overall, this study demonstrates a reliable strategy to access mono- and heterodinuclear cage complexes and illustrates its utility through a photocatalytic proof-of-concept study.
{"title":"Confined Metal Centers in a Symmetric Cage: Mono- and Heterodinuclear Complexes for Photocatalytic Hydrogen Evolution","authors":"Melvin Raulin, Federico Droghetti, Davide Zeppilli, Federico Begato, Pradip Kumar Mondal, Marzio Rancan, Giulia Licini, Laura Orian, Mirco Natali, Cristiano Zonta","doi":"10.1039/d5qi02424b","DOIUrl":"https://doi.org/10.1039/d5qi02424b","url":null,"abstract":"We report a selective metallation strategy that enables the controlled incorporation of one or two distinct metal ions within a chiral and symmetric tris(2-pyridylmethyl)amine (<strong>TPMA</strong>)-based molecular cage. Unlike typical homoditopic ligands, which often lead to scrambling and statistical mixtures, our approach affords well-defined mononuclear (<strong>CoH</strong><small><sub><strong>4</strong></sub></small>) and heterodinuclear (<strong>CoZn</strong>, <strong>CoCu</strong>) complexes in a straightforward and reproducible manner. This represents a rare example of heterometallic cage complexes from a symmetric scaffold, where the stepwise addition of metal ions affords well-defined mono- and dinuclear species. To illustrate the functional relevance of this strategy, we evaluated the photocatalytic hydrogen evolution activity of the different mono- and dinuclear complexes. The results reveal that the mononuclear <strong>CoH</strong><small><sub><strong>4</strong></sub></small> cage displays the highest performance, which we propose to arise from second-sphere proton transfer facilitated by the non-coordinated <strong>TPMA</strong> unit. Complementary DFT calculations support this mechanistic hypothesis. Overall, this study demonstrates a reliable strategy to access mono- and heterodinuclear cage complexes and illustrates its utility through a photocatalytic proof-of-concept study.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993171","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}
Víctor Karim Abdelkader-Fernández, Mikel Garcia, Antonio Pérez-Romero, Francisco J Garcia Ruiz, Andres Godoy, Manuel Perez-Mendoza, Miguel Angel Galindo Cuesta
The precise spatial organization of metal species on carbon nanotube (CNT) surfaces is crucial for tailoring their electronic and dielectric properties, yet remains difficult to achieve in a controlled manner. Here, we report a CNT-based nanohybrid in which one-dimensional Pd(II) arrays, templated by single-stranded DNA (dA₁₅), are covalently anchored onto carboxyl-functionalized multi-walled CNTs. Building on our previous demonstration of continuous helical Pd–DNA architectures, we translate this structural precision to CNT surfaces, yielding uniformly decorated nanotube scaffolds. Comprehensive spectroscopic and microscopic analyses (FTIR, UV–Vis, TEM/HRTEM, EDS) confirm successful assembly and nanoscale organization. Electrical impedance spectroscopy reveals that the resulting CNT–DNA–Pd hybrid exhibits a distinct, tunable dielectric response compared to its individual components. This approach provides a versatile strategy for integrating programmable DNA-based metal architectures with carbon nanomaterials for potential applications in electronics and energy-related devices.
{"title":"Tunable Dielectric Nanoarchitectonics in Carbon Nanotubes via DNA-Directed Pd(II) Nanoarrays","authors":"Víctor Karim Abdelkader-Fernández, Mikel Garcia, Antonio Pérez-Romero, Francisco J Garcia Ruiz, Andres Godoy, Manuel Perez-Mendoza, Miguel Angel Galindo Cuesta","doi":"10.1039/d5qi02340h","DOIUrl":"https://doi.org/10.1039/d5qi02340h","url":null,"abstract":"The precise spatial organization of metal species on carbon nanotube (CNT) surfaces is crucial for tailoring their electronic and dielectric properties, yet remains difficult to achieve in a controlled manner. Here, we report a CNT-based nanohybrid in which one-dimensional Pd(II) arrays, templated by single-stranded DNA (dA₁₅), are covalently anchored onto carboxyl-functionalized multi-walled CNTs. Building on our previous demonstration of continuous helical Pd–DNA architectures, we translate this structural precision to CNT surfaces, yielding uniformly decorated nanotube scaffolds. Comprehensive spectroscopic and microscopic analyses (FTIR, UV–Vis, TEM/HRTEM, EDS) confirm successful assembly and nanoscale organization. Electrical impedance spectroscopy reveals that the resulting CNT–DNA–Pd hybrid exhibits a distinct, tunable dielectric response compared to its individual components. This approach provides a versatile strategy for integrating programmable DNA-based metal architectures with carbon nanomaterials for potential applications in electronics and energy-related devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"53 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968975","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}
Wenjing Zhang, Yumeng Cui, Siyu Li, Bingbing Zhang, Ying Wang
The development of high-performance ultraviolet (UV) nonlinear optical (NLO) crystals relies on the exploration of functional units. In this work, we investigate the [C2N4H7S] moiety as a promising candidate. By employing distinct non-π-conjugated anionic templates ([NH2SO3] and [BF4]), we successfully synthesized two crystals: non-centrosymmetric (NCS) (C2N4H7S)SO3NH2 and centrosymmetric (CS) (C2N4H7S)BF4. The former exhibits a significant second-harmonic generation (SHG) response 1.8 times that of KDP, while the latter shows a large birefringence of 0.500 at 546 nm. This study not only confirms the great potential of the [C2N4H7S] cation for UV NLO applications but also demonstrates how anionic selection dictates the macroscopic symmetry and resultant optical properties.
{"title":"Synergism of [C2N4H7S] cations and anionic modulators: tailoring second-order nonlinear optics and birefringence in organic–inorganic crystals","authors":"Wenjing Zhang, Yumeng Cui, Siyu Li, Bingbing Zhang, Ying Wang","doi":"10.1039/d5qi02445e","DOIUrl":"https://doi.org/10.1039/d5qi02445e","url":null,"abstract":"The development of high-performance ultraviolet (UV) nonlinear optical (NLO) crystals relies on the exploration of functional units. In this work, we investigate the [C<small><sub>2</sub></small>N<small><sub>4</sub></small>H<small><sub>7</sub></small>S] moiety as a promising candidate. By employing distinct non-π-conjugated anionic templates ([NH<small><sub>2</sub></small>SO<small><sub>3</sub></small>] and [BF<small><sub>4</sub></small>]), we successfully synthesized two crystals: non-centrosymmetric (NCS) (C<small><sub>2</sub></small>N<small><sub>4</sub></small>H<small><sub>7</sub></small>S)SO<small><sub>3</sub></small>NH<small><sub>2</sub></small> and centrosymmetric (CS) (C<small><sub>2</sub></small>N<small><sub>4</sub></small>H<small><sub>7</sub></small>S)BF<small><sub>4</sub></small>. The former exhibits a significant second-harmonic generation (SHG) response 1.8 times that of KDP, while the latter shows a large birefringence of 0.500 at 546 nm. This study not only confirms the great potential of the [C<small><sub>2</sub></small>N<small><sub>4</sub></small>H<small><sub>7</sub></small>S] cation for UV NLO applications but also demonstrates how anionic selection dictates the macroscopic symmetry and resultant optical properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"61 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995931","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}
Near-infrared phosphor-converted light-emitting diodes have significant applications in biomedical imaging, night vision technology, industrial inspection, and spectral analysis. Typical phosphors, constituted with isolated Cr3+ ions and homogeneous Cr3+−Cr3+ ion pairs, represent the predominant strategy for facilitating efficient NIR emission. Nonetheless, this methodology requires extensive doping of Cr3+, leading to luminescent quenching and significant lattice distortion. Here, a heterogeneous ion pair (Mn2+-Cr3+) co-doping strategy was proposed to construct an ultra-efficient energy transfer from Mn2+ to Cr3+, and boost the NIR emission in trace Cr3+-doped hexagonal aluminate phosphors LaMgAl11O19:Cr3+. The formation of Mn2+-Cr3+ heterogeneous ion pairs was forecasted through in-depth structural and theoretical calculations and was then further demonstrated by electron paramagnetic resonance, X-ray photoelectron spectroscopy, and photoluminescence analysis. Notably, the Mn2+-Cr3+ heterogeneous ion pairs in LaMgAl11O19 could realize an ultimate energy transfer efficiency of 100%, resulting in a record NIR quantum efficiency (IQE~100%) in trace Cr3+ (0.5 mol%) doping. A high output power (134 mW@350 mA) NIR pc-LED and a high color rendering full-spectrum pc-LED (CRI = 90.0) were simultaneously realized based on LaMgAl11O19:Mn2+, Cr3+. This novel perspective on the heterogeneous ion pair offers an enriched understanding of the underlying design principles and facilitates the exploration of innovative NIR emitting phosphors.
{"title":"Ultra-efficient energy transfer and near-infrared luminescence in hexagonal aluminate phosphors enabled by heterogeneous ion pairs co-doping","authors":"Xiaoyi Liu, Zhaojiang Liu, Yujuan Dong, Chuang Wang, Yichao Wang, Ge Zhu, Shuangyu Xin","doi":"10.1039/d5qi02197a","DOIUrl":"https://doi.org/10.1039/d5qi02197a","url":null,"abstract":"Near-infrared phosphor-converted light-emitting diodes have significant applications in biomedical imaging, night vision technology, industrial inspection, and spectral analysis. Typical phosphors, constituted with isolated Cr3+ ions and homogeneous Cr3+−Cr3+ ion pairs, represent the predominant strategy for facilitating efficient NIR emission. Nonetheless, this methodology requires extensive doping of Cr3+, leading to luminescent quenching and significant lattice distortion. Here, a heterogeneous ion pair (Mn2+-Cr3+) co-doping strategy was proposed to construct an ultra-efficient energy transfer from Mn2+ to Cr3+, and boost the NIR emission in trace Cr3+-doped hexagonal aluminate phosphors LaMgAl11O19:Cr3+. The formation of Mn2+-Cr3+ heterogeneous ion pairs was forecasted through in-depth structural and theoretical calculations and was then further demonstrated by electron paramagnetic resonance, X-ray photoelectron spectroscopy, and photoluminescence analysis. Notably, the Mn2+-Cr3+ heterogeneous ion pairs in LaMgAl11O19 could realize an ultimate energy transfer efficiency of 100%, resulting in a record NIR quantum efficiency (IQE~100%) in trace Cr3+ (0.5 mol%) doping. A high output power (134 mW@350 mA) NIR pc-LED and a high color rendering full-spectrum pc-LED (CRI = 90.0) were simultaneously realized based on LaMgAl11O19:Mn2+, Cr3+. This novel perspective on the heterogeneous ion pair offers an enriched understanding of the underlying design principles and facilitates the exploration of innovative NIR emitting phosphors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"267 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962198","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}
Yu-Xuan Wang, Ming-Yu Guo, Tong Xie, Lin Chen, De-Xuan Liu, Wei-Xiong Zhang, Guo-Ming Wang
Photoluminescence (PL) switchable materials have become an important class of intelligent materials for promising applications in sensors, anti-counterfeit and information storage. A longstanding challenge lies in the rational design of highcontrast, quick-response and reversible PL switch. Herein, we present a new organic-inorganic hybrid metal halide crystal, (C9H13N2O)2MnCl4 (1), which undergoes two-step P1 (1α)-P1 (1TS)-I42d (1β) phase transitions at 378 K and 423 K during heating process, accompanied by PL colour changes from red in 1α, to orange in 1TS and green in 1β, respectively. Moreover, 1β could controllably return to 1α under different humidity conditions. Detailed structural studies reveal that the reversible transition is driven by the breaking and reformation of Mn-O bonds between C9H13N2O + cations and Mn 2+ . In convenience of the good cyclability and high sensitivity of such phase-transition induced PL transformation, we designed different models to demonstrate the application in optical encryption. This work provides a new insight for designing stimulus-responsive luminescent materials through dynamic chemical bonding for advanced optical materials with tenable and recoverable properties.
{"title":"Reversible Red-green Photoluminescence Transformation Induced by Dynamic Coordination Bonds in a Phase-transition Hybrid Crystal","authors":"Yu-Xuan Wang, Ming-Yu Guo, Tong Xie, Lin Chen, De-Xuan Liu, Wei-Xiong Zhang, Guo-Ming Wang","doi":"10.1039/d5qi02518d","DOIUrl":"https://doi.org/10.1039/d5qi02518d","url":null,"abstract":"Photoluminescence (PL) switchable materials have become an important class of intelligent materials for promising applications in sensors, anti-counterfeit and information storage. A longstanding challenge lies in the rational design of highcontrast, quick-response and reversible PL switch. Herein, we present a new organic-inorganic hybrid metal halide crystal, (C9H13N2O)2MnCl4 (1), which undergoes two-step P1 (1α)-P1 (1TS)-I42d (1β) phase transitions at 378 K and 423 K during heating process, accompanied by PL colour changes from red in 1α, to orange in 1TS and green in 1β, respectively. Moreover, 1β could controllably return to 1α under different humidity conditions. Detailed structural studies reveal that the reversible transition is driven by the breaking and reformation of Mn-O bonds between C9H13N2O + cations and Mn 2+ . In convenience of the good cyclability and high sensitivity of such phase-transition induced PL transformation, we designed different models to demonstrate the application in optical encryption. This work provides a new insight for designing stimulus-responsive luminescent materials through dynamic chemical bonding for advanced optical materials with tenable and recoverable properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"124 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993175","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}
Vanessa Rück, Hiroki Kanazawa, Zhiyu Huang, Christian Brinch Mollerup, Leila Lo Leggio, Jiro Kondo, Tom Vosch
Significant efforts have been invested in unraveling the stucture-property relationship of DNA-AgNCs using relatively short DNA sequences. Due to the limited sequence length, two or more strands are often required to stabilize a DNA-AgNC. Therefore, functionalization inherently introduces multiple reactive sites, hindering the implementation of single-site linking strategies. Here, we exploit the concept of using an inert thymine linking segment to connect two small DNA strands to develop a single-strand version of a DNA₂-[Ag₁₆Cl₂]⁸⁺. Our results demonstrate that these redesigned constructs preserve the core AgNC structure and photophysical properties, while enabling future single-site functionalization. Furthermore, this approach allows experimental confirmation of the inertness of thymine linking segments towards silver.
{"title":"Bridging the gap: thymine segments to create single-strand versions of DNA2-[Ag₁₆Cl₂]8+","authors":"Vanessa Rück, Hiroki Kanazawa, Zhiyu Huang, Christian Brinch Mollerup, Leila Lo Leggio, Jiro Kondo, Tom Vosch","doi":"10.1039/d5qi02482j","DOIUrl":"https://doi.org/10.1039/d5qi02482j","url":null,"abstract":"Significant efforts have been invested in unraveling the stucture-property relationship of DNA-AgNCs using relatively short DNA sequences. Due to the limited sequence length, two or more strands are often required to stabilize a DNA-AgNC. Therefore, functionalization inherently introduces multiple reactive sites, hindering the implementation of single-site linking strategies. Here, we exploit the concept of using an inert thymine linking segment to connect two small DNA strands to develop a single-strand version of a DNA₂-[Ag₁₆Cl₂]⁸⁺. Our results demonstrate that these redesigned constructs preserve the core AgNC structure and photophysical properties, while enabling future single-site functionalization. Furthermore, this approach allows experimental confirmation of the inertness of thymine linking segments towards silver.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955860","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}
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