Christina Siakalli, Bradley Edward Osborne, Ryan Brown, Claudia Rocco, Dominik Weiss, Enrique García-España, Pascal Grundler, Anzhelika Moiseeva, Zeynep Talip, Nicholas P. van der Meulen, Michelle Ma, Nicholas J Long
Emerging therapeutic radiolanthanides have utility for systemic molecular radiotherapy in nuclear medicine, provided that suitable chemical technology is available to incorporate them into receptor-targeted radiopharmaceuticals. In this work, N,N’-bis(8-hydroxyquinoline-2-ylmethyl)-4,13-diaza-18-crown-6 (H2KHQ) was synthesised, and its binding ability, thermodynamic stability and selectivity for Ln3+ ions (Ln3+ = La, Tb, and Lu) investigated. The design of H2KHQ involves pendant arms featuring 8-hydroxyquinoline units, known to possess metal-chelating properties and desirable activity in other therapeutic molecules. H2KHQ exhibited selectivity for the larger Ln3+ ions, confirmed by experimentally measured stability constants as well as DFT calculations. H2KHQ was able to bind the larger, non-radioactive La3+ and Tb3+ ions within 30 minutes at room temperature, forming a single, 2-fold symmetric species in solution. The structure of [La-HKHQ]2+, as determined by single crystal XRD, emphasized the need for high denticity chelators to satisfy the coordination sphere of the Ln3+, showing a 10-coordinate La3+ metal centre. H2KHQ was radiolabelled with [161Tb]TbCl3 under mild conditions in 92 % radiochemical yield in promising proof-of-concept measurements.
{"title":"Hydroxyquinoline-functionalised aza-crown macrocycles for lanthanide coordination","authors":"Christina Siakalli, Bradley Edward Osborne, Ryan Brown, Claudia Rocco, Dominik Weiss, Enrique García-España, Pascal Grundler, Anzhelika Moiseeva, Zeynep Talip, Nicholas P. van der Meulen, Michelle Ma, Nicholas J Long","doi":"10.1039/d5dt03015c","DOIUrl":"https://doi.org/10.1039/d5dt03015c","url":null,"abstract":"Emerging therapeutic radiolanthanides have utility for systemic molecular radiotherapy in nuclear medicine, provided that suitable chemical technology is available to incorporate them into receptor-targeted radiopharmaceuticals. In this work, N,N’-bis(8-hydroxyquinoline-2-ylmethyl)-4,13-diaza-18-crown-6 (H2KHQ) was synthesised, and its binding ability, thermodynamic stability and selectivity for Ln3+ ions (Ln3+ = La, Tb, and Lu) investigated. The design of H2KHQ involves pendant arms featuring 8-hydroxyquinoline units, known to possess metal-chelating properties and desirable activity in other therapeutic molecules. H2KHQ exhibited selectivity for the larger Ln3+ ions, confirmed by experimentally measured stability constants as well as DFT calculations. H2KHQ was able to bind the larger, non-radioactive La3+ and Tb3+ ions within 30 minutes at room temperature, forming a single, 2-fold symmetric species in solution. The structure of [La-HKHQ]2+, as determined by single crystal XRD, emphasized the need for high denticity chelators to satisfy the coordination sphere of the Ln3+, showing a 10-coordinate La3+ metal centre. H2KHQ was radiolabelled with [161Tb]TbCl3 under mild conditions in 92 % radiochemical yield in promising proof-of-concept measurements.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070569","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}
Broadband near-infrared (NIR) phosphors activated by Cr3+ are pivotal for next-generation NIR light sources, yet achieving long-wavelength NIR emission remains challenging. Herein, we report a strategy of tailoring spin-paired Cr3+ ion dimers in a spinel-type LiZn0.6Mg0.4SbO4 host to achieve extended broadband NIR emission. Heavy Cr3+ doping, inducing spin-paired Cr3+ ion dimers, coupled with crystal-field engineering shifts the original 709 nm narrow-band emission to 860 nm (via Mg2+ incorporation) and further to 970 nm broadband emission (via Ca2+ incorporation). The optimized phosphor exhibits a 1.8-fold enhancement in thermal stability and a 1.35-fold increase in internal quantum efficiency compared to its Mg-free counterpart. Fabricated NIR phosphor-converted light-emitting diode (pc-LED) delivers an output power of 40.97 mW at 750 mA, demonstrating promising potential in versatile photonics applications. This work provides a viable approach for designing broadband NIR phosphors through precise manipulation of exchange-coupled Cr3+ ion dimers.
{"title":"Tailoring Spin-Paired Cr3+ Dimers in a Spinel Host for Giant-Tunable and Enhanced Near-Infrared Emission","authors":"Jia Yang, Yahong Jin","doi":"10.1039/d5dt02984h","DOIUrl":"https://doi.org/10.1039/d5dt02984h","url":null,"abstract":"Broadband near-infrared (NIR) phosphors activated by Cr3+ are pivotal for next-generation NIR light sources, yet achieving long-wavelength NIR emission remains challenging. Herein, we report a strategy of tailoring spin-paired Cr3+ ion dimers in a spinel-type LiZn0.6Mg0.4SbO4 host to achieve extended broadband NIR emission. Heavy Cr3+ doping, inducing spin-paired Cr3+ ion dimers, coupled with crystal-field engineering shifts the original 709 nm narrow-band emission to 860 nm (via Mg2+ incorporation) and further to 970 nm broadband emission (via Ca2+ incorporation). The optimized phosphor exhibits a 1.8-fold enhancement in thermal stability and a 1.35-fold increase in internal quantum efficiency compared to its Mg-free counterpart. Fabricated NIR phosphor-converted light-emitting diode (pc-LED) delivers an output power of 40.97 mW at 750 mA, demonstrating promising potential in versatile photonics applications. This work provides a viable approach for designing broadband NIR phosphors through precise manipulation of exchange-coupled Cr3+ ion dimers.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"70 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048693","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}
Meriem Goudjil, Laura Chelazzi, Mauro Perfetti, Leonardo Tacconi, Carlo Andrea Mattei
We report an unprecedented one-pot route synthesis and in-depth characterizations of a new binuclear copper(II) complex with the tridentate PAN ligand (1-(2-pyridylazo)-2-naphthol). The compound of formula [Cu2(μ-SO4)(PAN)2(H2O)2] was isolated as a highly crystalline material, where the two copper(II) centers are connected by a sulfate bridge. Singlecrystal X-ray diffraction (SC-XRD) combined with UV-Vis spectroscopy and EPR confirms a square-pyramidal coordination around each Cu(II) center in both the solid state and solution. Hirshfeld surface analysis provided a quantitative visualization of intermolecular interactions, such as O•••H bonding and π-π stacking, and their contributions to stabilizing the crystal lattice. Remarkably, magnetic studies revealed an unconventional slow magnetic relaxation under applied dc fields, characterized by three field-dependent processes spanning more than four orders of magnitude in frequency. These findings broaden the design space of transition-metal molecular magnets by showing that simple sulfate bridging and π-conjugated ligands can engender complex relaxation dynamics in Cu(II) dimers.
{"title":"Unusual Slow Magnetic Relaxation in a Sulfate-Bridged Copper (II) Complex with 1-(2-Pyridylazo)-2-Naphthol Ligand","authors":"Meriem Goudjil, Laura Chelazzi, Mauro Perfetti, Leonardo Tacconi, Carlo Andrea Mattei","doi":"10.1039/d6dt00068a","DOIUrl":"https://doi.org/10.1039/d6dt00068a","url":null,"abstract":"We report an unprecedented one-pot route synthesis and in-depth characterizations of a new binuclear copper(II) complex with the tridentate PAN ligand (1-(2-pyridylazo)-2-naphthol). The compound of formula [Cu2(μ-SO4)(PAN)2(H2O)2] was isolated as a highly crystalline material, where the two copper(II) centers are connected by a sulfate bridge. Singlecrystal X-ray diffraction (SC-XRD) combined with UV-Vis spectroscopy and EPR confirms a square-pyramidal coordination around each Cu(II) center in both the solid state and solution. Hirshfeld surface analysis provided a quantitative visualization of intermolecular interactions, such as O•••H bonding and π-π stacking, and their contributions to stabilizing the crystal lattice. Remarkably, magnetic studies revealed an unconventional slow magnetic relaxation under applied dc fields, characterized by three field-dependent processes spanning more than four orders of magnitude in frequency. These findings broaden the design space of transition-metal molecular magnets by showing that simple sulfate bridging and π-conjugated ligands can engender complex relaxation dynamics in Cu(II) dimers.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"72 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048666","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}
Xin-Feng Li, Hao Wang, Du-Yong Chen, Qiang Liu, Jingyi Xiao, Wen Wen, Wen-Jing Jiang, Liang Zhao, Yin-Shan Meng, Tao Liu
Multi-channel bistable materials have emerged as compelling candidates for applications in information encryption and smart devices. However, achieving systems that simultaneously exhibit tunable transitions and pronounced thermal hysteresis remains a formidable challenge. In this work, we introduce a ligand-modulation strategy wherein subtle substituent modifications precisely regulate intermolecular interactions, thereby enabling a controllable transformation from a one-step spin-crossover (SCO) transition in {[(Tp)FeIII(CN)3][FeII0.5(L1)]} (1) to a two-step transition in {[(Tp)FeIII(CN)3][FeII0.5(L2)]} (2) (L1 = 5-pyridin-4-ylthiophene-2-carboxaldehyde, L2 = 1-(5-pyridin-4-ylthiophen-2-yl)ethanone), accompanied by thermal hysteresis. Remarkably, the stepwise transitions and their associated hysteresis were concurrently manifested in optical absorption and dielectric responses, demonstrating cooperative multistate modulation across photonic, magnetic, and electronic channels. This study, therefore, establishes a viable molecular-level approach for realizing tunable stepwise transitions with thermally hysteretic behavior in multiple-channel functionalities, paving the way for the development of next-generation multifunctional switchable materials and devices.
{"title":"Modulating multi-channel bistability in cyanide-bridged {Fe<sub>2</sub>Fe} spin-crossover coordination polymers.","authors":"Xin-Feng Li, Hao Wang, Du-Yong Chen, Qiang Liu, Jingyi Xiao, Wen Wen, Wen-Jing Jiang, Liang Zhao, Yin-Shan Meng, Tao Liu","doi":"10.1039/d5dt02923f","DOIUrl":"https://doi.org/10.1039/d5dt02923f","url":null,"abstract":"<p><p>Multi-channel bistable materials have emerged as compelling candidates for applications in information encryption and smart devices. However, achieving systems that simultaneously exhibit tunable transitions and pronounced thermal hysteresis remains a formidable challenge. In this work, we introduce a ligand-modulation strategy wherein subtle substituent modifications precisely regulate intermolecular interactions, thereby enabling a controllable transformation from a one-step spin-crossover (SCO) transition in {[(Tp)Fe<sup>III</sup>(CN)<sub>3</sub>][Fe<sup>II</sup><sub>0.5</sub>(L1)]} (1) to a two-step transition in {[(Tp)Fe<sup>III</sup>(CN)<sub>3</sub>][Fe<sup>II</sup><sub>0.5</sub>(L2)]} (2) (L1 = 5-pyridin-4-ylthiophene-2-carboxaldehyde, L2 = 1-(5-pyridin-4-ylthiophen-2-yl)ethanone), accompanied by thermal hysteresis. Remarkably, the stepwise transitions and their associated hysteresis were concurrently manifested in optical absorption and dielectric responses, demonstrating cooperative multistate modulation across photonic, magnetic, and electronic channels. This study, therefore, establishes a viable molecular-level approach for realizing tunable stepwise transitions with thermally hysteretic behavior in multiple-channel functionalities, paving the way for the development of next-generation multifunctional switchable materials and devices.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146049510","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}
Son N. T. Phan, João V. Schober, Judy I. Wu, Thomas S. Teets
Herein, we report a series of three bis-cyclometalated iridium(III) complexes each bearing an arylacetylide and an N-heterocyclic carbene (NHC) ligand. The cyclometalating ligand is 2-(2,4-difluorophenyl)pyrazole (F2ppz), chosen to ensure the 5d(Ir) → π*(F2ppz) 3MLCT excited-state is higher in energy than the 3(π → π*) state of the acetylide, allowing luminescence to originate from the latter. The strong-field NHC is included to alleviate photoluminescence (PL) quenching caused by the thermal population of the triplet metal-centered (3MC) states, but nevertheless, the three compounds are weakly luminescent. The parent phenylacetylide complex only emits blue luminescence in dichloromethane solution at 77 K, with a peak wavelength of 424 nm. Complexes bearing substituted phenylacetylides that engender emission in the green and yellow regions are also not emissive in solution at room temperature, but phosphoresce weakly in poly(methylmethacrylate) film and also emit at 77 K in solution. Since the emissive excited states in these compounds are acetylide-localized, we tested whether cyclometalating ligands are needed at all by preparing a new 1,2,3,4,5-pentamethylcyclopentadienyl Ir(III) acetylide complex, but this complex does not luminesce under any of the conditions tested. The four reported complexes are structurally characterized by multinuclear NMR and one of them by single-crystal X-ray diffraction. Thorough electrochemical and photophysical studies of the complexes were also carried out, complemented by time-dependent density functional theory (TD-DFT) calculations.
{"title":"Synthesis and photoluminescence of iridium(III) arylacetylide complexes with acetylide-localized emissive excited states","authors":"Son N. T. Phan, João V. Schober, Judy I. Wu, Thomas S. Teets","doi":"10.1039/d5dt02734a","DOIUrl":"https://doi.org/10.1039/d5dt02734a","url":null,"abstract":"Herein, we report a series of three bis-cyclometalated iridium(<small>III</small>) complexes each bearing an arylacetylide and an N-heterocyclic carbene (NHC) ligand. The cyclometalating ligand is 2-(2,4-difluorophenyl)pyrazole (F<small><sub>2</sub></small>ppz), chosen to ensure the 5d(Ir) → π*(F<small><sub>2</sub></small>ppz) <small><sup>3</sup></small>MLCT excited-state is higher in energy than the <small><sup>3</sup></small>(π → π*) state of the acetylide, allowing luminescence to originate from the latter. The strong-field NHC is included to alleviate photoluminescence (PL) quenching caused by the thermal population of the triplet metal-centered (<small><sup>3</sup></small>MC) states, but nevertheless, the three compounds are weakly luminescent. The parent phenylacetylide complex only emits blue luminescence in dichloromethane solution at 77 K, with a peak wavelength of 424 nm. Complexes bearing substituted phenylacetylides that engender emission in the green and yellow regions are also not emissive in solution at room temperature, but phosphoresce weakly in poly(methylmethacrylate) film and also emit at 77 K in solution. Since the emissive excited states in these compounds are acetylide-localized, we tested whether cyclometalating ligands are needed at all by preparing a new 1,2,3,4,5-pentamethylcyclopentadienyl Ir(<small>III</small>) acetylide complex, but this complex does not luminesce under any of the conditions tested. The four reported complexes are structurally characterized by multinuclear NMR and one of them by single-crystal X-ray diffraction. Thorough electrochemical and photophysical studies of the complexes were also carried out, complemented by time-dependent density functional theory (TD-DFT) calculations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"31 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048853","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 the present work, a series of Eu2+-doped Sr5(PO4)3Cl powders with varying Eu content was synthesized by the molten salt method in an air atmosphere. The self-reduction of Eu3+ to Eu2+ occurred during the phase transformation of starting Sr3(PO4)2:Eu to Sr5(PO4)3Cl:Eu in molten SrCl2. The synthesis conditions were optimized in terms of reaction temperature, time, and precursor-to-flux ratio. The optical properties of the obtained materials were investigated through photoluminescence, thermally stimulated luminescence, and persistent luminescence decay measurements. Regardless of the Eu concentration, the resulting powders possessed a dominating Eu2+-related broadband emission with a maximum at 445 nm; however, significantly weaker emission in the red region was also detected, suggesting incomplete reduction of Eu3+ to Eu2+. Minor emission tunability was achieved by varying the excitation wavelength, which allows for the elimination of Eu3+ emission. The analysis of trap properties indicated the presence of two types of traps. Although all obtained Ea values were deep, a weak persistent luminescence signal of Eu2+ can be detected for several hours after X-ray irradiation.
{"title":"Molten salt synthesis of Eu2+-doped Sr5(PO4)3Cl in air atmosphere: europium self-reduction and optical properties.","authors":"Simona Bendziute,Jonas Stadulis,Guna Doke,Guna Krieke,Andris Antuzevics,Vladimir Pankratov,Inga Grigoraviciute,Arturas Katelnikovas,Aleksej Zarkov","doi":"10.1039/d5dt02634b","DOIUrl":"https://doi.org/10.1039/d5dt02634b","url":null,"abstract":"In the present work, a series of Eu2+-doped Sr5(PO4)3Cl powders with varying Eu content was synthesized by the molten salt method in an air atmosphere. The self-reduction of Eu3+ to Eu2+ occurred during the phase transformation of starting Sr3(PO4)2:Eu to Sr5(PO4)3Cl:Eu in molten SrCl2. The synthesis conditions were optimized in terms of reaction temperature, time, and precursor-to-flux ratio. The optical properties of the obtained materials were investigated through photoluminescence, thermally stimulated luminescence, and persistent luminescence decay measurements. Regardless of the Eu concentration, the resulting powders possessed a dominating Eu2+-related broadband emission with a maximum at 445 nm; however, significantly weaker emission in the red region was also detected, suggesting incomplete reduction of Eu3+ to Eu2+. Minor emission tunability was achieved by varying the excitation wavelength, which allows for the elimination of Eu3+ emission. The analysis of trap properties indicated the presence of two types of traps. Although all obtained Ea values were deep, a weak persistent luminescence signal of Eu2+ can be detected for several hours after X-ray irradiation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044698","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}
V. Arjun, K. P. Muthukumaran, A. Nithya, M. Yoshimura, S. Karuppuchamy
The incorporation of p-type semiconductor materials into perovskites is one of the most preferable methods for improving the perovskite layer quality, suppressing carrier recombination and achieving remarkable photovoltaic performance and stability in perovskite solar cells. Herein, NiO-g-C3N4 nanocomposites are incorporated with a methylammonium lead iodide (MAPI) precursor to assist in the formation of a high-quality perovskite layer with large grains and fewer defects. The incorporation of NiO-g-C3N4 facilitates superior charge generation and charge transfer, reduces recombination at the interface and increases the light harvesting ability by improving the MAPI layer formation and modifying the band position of MAPI. The power conversion efficiency (PCE) of the NiO-g-C3N4-MAPI-based PSC increased from 8% to 14%. The maximum PCE of 14.72% was obtained with improved photovoltaic parameters, i.e., a current density (Jsc) of 22.56 mA cm−2, an open circuit voltage (Voc) of 0.96 V and a fill factor (FF) of 0.68, for the NiO-g-C3N4 (1 : 0.5)-MAPI-based PSC. The NiO-g-C3N4-MAPI-based PSCs showed improved stability after 600 hours of storage in an ambient atmosphere.
{"title":"Hole transport material free-NiO-g-C3N4-incorporated methylammonium lead iodide-based perovskite solar cells","authors":"V. Arjun, K. P. Muthukumaran, A. Nithya, M. Yoshimura, S. Karuppuchamy","doi":"10.1039/d5dt02401c","DOIUrl":"https://doi.org/10.1039/d5dt02401c","url":null,"abstract":"The incorporation of p-type semiconductor materials into perovskites is one of the most preferable methods for improving the perovskite layer quality, suppressing carrier recombination and achieving remarkable photovoltaic performance and stability in perovskite solar cells. Herein, NiO-g-C<small><sub>3</sub></small>N<small><sub>4</sub></small> nanocomposites are incorporated with a methylammonium lead iodide (MAPI) precursor to assist in the formation of a high-quality perovskite layer with large grains and fewer defects. The incorporation of NiO-g-C<small><sub>3</sub></small>N<small><sub>4</sub></small> facilitates superior charge generation and charge transfer, reduces recombination at the interface and increases the light harvesting ability by improving the MAPI layer formation and modifying the band position of MAPI. The power conversion efficiency (PCE) of the NiO-g-C<small><sub>3</sub></small>N<small><sub>4</sub></small>-MAPI-based PSC increased from 8% to 14%. The maximum PCE of 14.72% was obtained with improved photovoltaic parameters, <em>i.e.</em>, a current density (<em>J</em><small><sub>sc</sub></small>) of 22.56 mA cm<small><sup>−2</sup></small>, an open circuit voltage (<em>V</em><small><sub>oc</sub></small>) of 0.96 V and a fill factor (FF) of 0.68, for the NiO-g-C<small><sub>3</sub></small>N<small><sub>4</sub></small> (1 : 0.5)-MAPI-based PSC. The NiO-g-C<small><sub>3</sub></small>N<small><sub>4</sub></small>-MAPI-based PSCs showed improved stability after 600 hours of storage in an ambient atmosphere.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"68 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044716","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}
Food spoilage arising from protein degradation and microbial activities leads to the release of biogenic amines (BAs) and volatile amines (VAs), which compromise its quality and pose health hazards. Conventional chromatographic techniques for monitoring BAs and VAs, for example, HPLC, GC and spectrometry-based methods, although accurate, are often costly and time-consuming and require sophisticated instrumentation and skilled operation, limiting their suitability for rapid and on-site detection. In contrast, reticular frameworks, including metal-organic frameworks (MOFs) and coordination polymers (CPs), have emerged over the past decade as promising optical probes for the detection of BAs and VAs, offering rapid response, operational simplicity, cost-effectiveness, excellent sensitivity through tunable host-guest interactions, and intriguing luminescence properties. In this review article, we first present an overview of the general chemistry and toxicological impacts of BAs and VAs, highlighting the urgent need for efficient amine detection strategies. Next, we outline the fundamentals of reticular chemistry, including design principles, controlling factors and synthetic strategies, that establish MOFs/CPs as robust sensing platforms. Subsequently, a dedicated section underscores optical detection mechanisms (fluorometric and colorimetric), alongside host-guest charge transfer and electron transfer principles. Thereafter, we vividly analyze recent MOFs/CPs and their composite materials, reported between 2015 and 2025, for detecting BAs and VAs, emphasizing their contribution to food quality monitoring. To conclude, we propose future avenues, integrating artificial intelligence, machine learning, and portable robotics with reticular materials to enhance real-world viability. Overall, this perspective article aims to provide specialists with a technical account of recent advances while enabling non-experts to grasp the fundamentals of sustainable food safety solutions.
{"title":"Recent advances in reticular frameworks and allied composite materials for ultrasensitive optical detection of biogenic and volatile amines in food spoilage monitoring.","authors":"Mohit Kumar Chattopadhyay,Udayan Mondal,Sourav Datta,Priyabrata Banerjee","doi":"10.1039/d5dt02612a","DOIUrl":"https://doi.org/10.1039/d5dt02612a","url":null,"abstract":"Food spoilage arising from protein degradation and microbial activities leads to the release of biogenic amines (BAs) and volatile amines (VAs), which compromise its quality and pose health hazards. Conventional chromatographic techniques for monitoring BAs and VAs, for example, HPLC, GC and spectrometry-based methods, although accurate, are often costly and time-consuming and require sophisticated instrumentation and skilled operation, limiting their suitability for rapid and on-site detection. In contrast, reticular frameworks, including metal-organic frameworks (MOFs) and coordination polymers (CPs), have emerged over the past decade as promising optical probes for the detection of BAs and VAs, offering rapid response, operational simplicity, cost-effectiveness, excellent sensitivity through tunable host-guest interactions, and intriguing luminescence properties. In this review article, we first present an overview of the general chemistry and toxicological impacts of BAs and VAs, highlighting the urgent need for efficient amine detection strategies. Next, we outline the fundamentals of reticular chemistry, including design principles, controlling factors and synthetic strategies, that establish MOFs/CPs as robust sensing platforms. Subsequently, a dedicated section underscores optical detection mechanisms (fluorometric and colorimetric), alongside host-guest charge transfer and electron transfer principles. Thereafter, we vividly analyze recent MOFs/CPs and their composite materials, reported between 2015 and 2025, for detecting BAs and VAs, emphasizing their contribution to food quality monitoring. To conclude, we propose future avenues, integrating artificial intelligence, machine learning, and portable robotics with reticular materials to enhance real-world viability. Overall, this perspective article aims to provide specialists with a technical account of recent advances while enabling non-experts to grasp the fundamentals of sustainable food safety solutions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"142 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044697","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}
Kelibinuer Wulamu, Ziting Yan, Dongdong Chu, Juanjuan Lu, Yanhui Zhang, Hong Du
This study focuses on hydroxyborates and employs a hydroxylation modification strategy to regulate the anionic framework of borates, leading to the successful synthesis of two novel hydroxyborates, namely, CsB(OH)4(H2O)2 and Na(NH4)2B10O16OH(H2O). With a ultraviolet (UV) cutoff edge below 200 nm, CsB(OH)4(H2O)2 possesses considerable potential for deep-ultraviolet (DUV) transmission applications. Notably, Na(NH4)2B10O16OH(H2O) represents a rare case of a hydroxyborates that contain two distinct fundamental building blocks (FBBs), namely [B5O10]5- and [B5O10(OH)]6-. In its structure, pseudo-layers constructed by 1∞[B5O9] chains alternate with those formed by 1∞[B5O9(OH)] chains, resulting in a structurally unique arrangement. Furthermore, Na(NH4)2B10O16OH(H2O) displays a large birefringence value of 0.074 at 546 nm, manifesting remarkable optical anisotropy—a key property for DUV polarization optical devices. Overall, these results demonstrate that the introduction of hydroxyl groups can effectively modulate the B-O framework and further enrich the structure diversity of borate-based optical materials.
{"title":"CsB(OH)4(H2O)2 and Na(NH4)2B10O16OH(H2O): Hydroxylation Modification Strategy Regulates the Borate Structures and Optical Properties","authors":"Kelibinuer Wulamu, Ziting Yan, Dongdong Chu, Juanjuan Lu, Yanhui Zhang, Hong Du","doi":"10.1039/d5dt02928g","DOIUrl":"https://doi.org/10.1039/d5dt02928g","url":null,"abstract":"This study focuses on hydroxyborates and employs a hydroxylation modification strategy to regulate the anionic framework of borates, leading to the successful synthesis of two novel hydroxyborates, namely, CsB(OH)4(H2O)2 and Na(NH4)2B10O16OH(H2O). With a ultraviolet (UV) cutoff edge below 200 nm, CsB(OH)4(H2O)2 possesses considerable potential for deep-ultraviolet (DUV) transmission applications. Notably, Na(NH4)2B10O16OH(H2O) represents a rare case of a hydroxyborates that contain two distinct fundamental building blocks (FBBs), namely [B5O10]5- and [B5O10(OH)]6-. In its structure, pseudo-layers constructed by 1∞[B5O9] chains alternate with those formed by 1∞[B5O9(OH)] chains, resulting in a structurally unique arrangement. Furthermore, Na(NH4)2B10O16OH(H2O) displays a large birefringence value of 0.074 at 546 nm, manifesting remarkable optical anisotropy—a key property for DUV polarization optical devices. Overall, these results demonstrate that the introduction of hydroxyl groups can effectively modulate the B-O framework and further enrich the structure diversity of borate-based optical materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"179 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044718","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}
Jing Han, Yue Hou, Yu Zhong, Yixuan Chen, Jianfei Xue, Yuejuan Zhang, Lei Gao, Yi Wan
To address always-on Ag+ release of Ag(I) complexes for antimicrobial treatment, infection microenvironment-responsive composites with high antimicrobial efficiency and on-demand Ag+ release were constructed by coating hyaluronic acid (HA) or Fe(III)-tannic acid complex (Fe(III)-TA) on a deliberately designed silver complex (1) with high silver content of 46.76 %，respectively. The targeted Ag+ leaching to eradicate bacteria was dependent on stimuli-responsive coating decomposition. Infection microenvironment cues, i.e. hyaluronidase (HAase) and acidity were used as endogenous triggers and wrapped complex 1 acted as carrier of antimicrobial Ag+. This smart design can avoid usage of additional carrier for antimicrobial agents in coventional reports and reduce its side effects of degradation into infection microenvironment. 1 was characterized with single crystal X-ray diffraction as a 1D chain assembled by Ag12 clusters. It showed effective broad-spectra antimicrobial activities with low minimal inhibition concentrations (MICs) originating from high Ag+ content. Under non-infection conditions, Ag+ release ratios of 1@HA and 1@Fe(III)-TA were suppressed significantly to 14.99 % and 3.31 %, respectively. In simulated infection microenvironment (1 wt % HAase or pH=5.5) they exhibited stimuli-switched coating disassembly leading to increased Ag+ releasing ratios of 59.26 % and 23.92 %, respectively. The moderate pH-induced Ag+ release of 1@Fe(III)-TA was attributed to partial cleavage of Fe-OH of Fe(III)-TA at pH=5.5, which was verified by pH-depended Ag+ release of 1@Fe(III)-TA . Stimuli-responsive coating deconstruction and antimicrobial performances of the two composites were confirmed by measurements of water contact angles, zeta potentials, inhibition zones and MICs. Specially, 1@Fe(III)-TA displayed more obvious acid-triggered performance for P. aeruginosa and carbapenem-resistant E. coli due to their stronger acid-producing. The successful integration of efficient antimicrobial Ag(I) complex with infection microenvironment-responsive coatings highlight its potential as a facile strategy for on-demand antimicrobial treatment at targeted bacterial infection.
{"title":"Infection microenvironment-responsive composites based on Ag(I) complex for targeted antimicrobial treatment","authors":"Jing Han, Yue Hou, Yu Zhong, Yixuan Chen, Jianfei Xue, Yuejuan Zhang, Lei Gao, Yi Wan","doi":"10.1039/d5dt02724a","DOIUrl":"https://doi.org/10.1039/d5dt02724a","url":null,"abstract":"To address always-on Ag+ release of Ag(I) complexes for antimicrobial treatment, infection microenvironment-responsive composites with high antimicrobial efficiency and on-demand Ag+ release were constructed by coating hyaluronic acid (HA) or Fe(III)-tannic acid complex (Fe(III)-TA) on a deliberately designed silver complex (1) with high silver content of 46.76 %，respectively. The targeted Ag+ leaching to eradicate bacteria was dependent on stimuli-responsive coating decomposition. Infection microenvironment cues, i.e. hyaluronidase (HAase) and acidity were used as endogenous triggers and wrapped complex 1 acted as carrier of antimicrobial Ag+. This smart design can avoid usage of additional carrier for antimicrobial agents in coventional reports and reduce its side effects of degradation into infection microenvironment. 1 was characterized with single crystal X-ray diffraction as a 1D chain assembled by Ag12 clusters. It showed effective broad-spectra antimicrobial activities with low minimal inhibition concentrations (MICs) originating from high Ag+ content. Under non-infection conditions, Ag+ release ratios of 1@HA and 1@Fe(III)-TA were suppressed significantly to 14.99 % and 3.31 %, respectively. In simulated infection microenvironment (1 wt % HAase or pH=5.5) they exhibited stimuli-switched coating disassembly leading to increased Ag+ releasing ratios of 59.26 % and 23.92 %, respectively. The moderate pH-induced Ag+ release of 1@Fe(III)-TA was attributed to partial cleavage of Fe-OH of Fe(III)-TA at pH=5.5, which was verified by pH-depended Ag+ release of 1@Fe(III)-TA . Stimuli-responsive coating deconstruction and antimicrobial performances of the two composites were confirmed by measurements of water contact angles, zeta potentials, inhibition zones and MICs. Specially, 1@Fe(III)-TA displayed more obvious acid-triggered performance for P. aeruginosa and carbapenem-resistant E. coli due to their stronger acid-producing. The successful integration of efficient antimicrobial Ag(I) complex with infection microenvironment-responsive coatings highlight its potential as a facile strategy for on-demand antimicrobial treatment at targeted bacterial infection.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146044717","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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