Soumalya Banerjee, Soumita Sarkar, Afsar Ali, Sunny Sarkar, Anjumun Rasool Ganie, Manzoor Ahmad Dar, Sasanka Dalapati, Astam K. Patra
2D Cerium phenylphosphonate nanosheets were prepared through a facile hydrothermal procedure. Analysis revealed monoclinic phase of cerium(IV)-bis(phenylphosphonate) with ultrathin sheet like morphology and +3 as well as +4 oxidation states of cerium. Notably, the nanosheets exhibited light absorption at around 325 nm, suggesting a band gap value of 3.0 eV. Mott-Schottky analysis provided additional insight, revealing a CB position at -0.123 VRHE and VB position at 2.877 VRHE. The photocurrent analysis and Nyquist plots demonstrated the nanosheets' ability to generate photoelectrons when exposed to light and effectively separate holes and electrons. The catalytic efficiency of the nanosheets was evaluated in a cycloaddition reaction involving several epoxides and CO2, resulting in the production of five-membered cyclic carbonates. Remarkably, in a solvent-free environment, the nanosheets achieved a product yield of over 90%. A series of meticulously controlled experiments were conducted to elucidate the mechanism, revealing that the reaction proceeds through a radical pathway. These findings indicate that these nanosheets can act as a highly efficient catalyst for the CO2 fixation reaction, displaying high yield, and recyclability.
{"title":"Ultrathin Cerium Phenylphosphonate Nanosheets for Photocatalytic Cycloaddition of Carbon Dioxide to Epoxides","authors":"Soumalya Banerjee, Soumita Sarkar, Afsar Ali, Sunny Sarkar, Anjumun Rasool Ganie, Manzoor Ahmad Dar, Sasanka Dalapati, Astam K. Patra","doi":"10.1039/d5dt02622a","DOIUrl":"https://doi.org/10.1039/d5dt02622a","url":null,"abstract":"2D Cerium phenylphosphonate nanosheets were prepared through a facile hydrothermal procedure. Analysis revealed monoclinic phase of cerium(IV)-bis(phenylphosphonate) with ultrathin sheet like morphology and +3 as well as +4 oxidation states of cerium. Notably, the nanosheets exhibited light absorption at around 325 nm, suggesting a band gap value of 3.0 eV. Mott-Schottky analysis provided additional insight, revealing a CB position at -0.123 VRHE and VB position at 2.877 VRHE. The photocurrent analysis and Nyquist plots demonstrated the nanosheets' ability to generate photoelectrons when exposed to light and effectively separate holes and electrons. The catalytic efficiency of the nanosheets was evaluated in a cycloaddition reaction involving several epoxides and CO2, resulting in the production of five-membered cyclic carbonates. Remarkably, in a solvent-free environment, the nanosheets achieved a product yield of over 90%. A series of meticulously controlled experiments were conducted to elucidate the mechanism, revealing that the reaction proceeds through a radical pathway. These findings indicate that these nanosheets can act as a highly efficient catalyst for the CO2 fixation reaction, displaying high yield, and recyclability.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145847196","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}
Dazhou Kuang, Sheng Yao, Yang Yang, Fangcai Zheng, Hui Wang
The efficient and durable oxygen evolution reaction (OER) electrocatalysts are critical for enhancing proton exchange membrane water electrolyzer (PEMWE) performance. RuO2 has high intrinsic OER activity, but it is susceptible to oxidation into soluble RuO4− species in acidic electrolyte due to the highly reactive nature of lattice oxygen. Herein, we introduce an effective strategy aimed at bolstering structural stability by constructing Ru/RuO2 heterostructures onto carbon nanotubes (Ru/RuO2@CNT). The formation of Ru0−O−Ru4+ interfacial structures within these heterostructures effectively suppresses the Ru4+ oxidation state and simultaneously refines the d-band center of Ru sites for optimizing intermediates adsorption, thus accelerating the OER kinetics. Consequently, the Ru/RuO2@CNT-300 achieves a low overpotential of 169 mV at 10 mA cm−2 and displays remarkable durability exceeding 100 hours of stable operation in a 0.5 M H2SO4. The unique structure endows the Ru/RuO2@CNT-300 with exceptional acidic OER activity compared to most reported electrocatalysts. This work provides a feasible pathway for designing efficient and stable OER electrocatalysts for high-performance PEMWE.
高效耐用的析氧反应（OER）电催化剂是提高质子交换膜水电解槽（PEMWE）性能的关键。RuO2具有较高的内在OER活性，但由于晶格氧的高活性，在酸性电解质中容易氧化成可溶的RuO4−。本文介绍了一种有效的策略，旨在通过在碳纳米管上构建Ru/RuO2异质结构来增强结构稳定性（Ru/RuO2@CNT）。这些异质结构中Ru0−O−Ru4+界面结构的形成有效地抑制了Ru4+的氧化态，同时细化了Ru位点的d波段中心，优化了中间体的吸附，从而加速了OER动力学。因此，Ru/RuO2@CNT-300在10 mA cm−2下实现了169 mV的低过电位，并在0.5 M H2SO4中表现出超过100小时的稳定运行。与大多数电催化剂相比，Ru/RuO2@CNT-300具有独特的酸性OER活性。本研究为设计高效稳定的OER电催化剂提供了可行的途径。
{"title":"Interface Engineering of Ru/RuO2 Heterostructures on Carbon Nanotubes for Efficient and Stable Acidic Oxygen Evolution","authors":"Dazhou Kuang, Sheng Yao, Yang Yang, Fangcai Zheng, Hui Wang","doi":"10.1039/d5dt02636a","DOIUrl":"https://doi.org/10.1039/d5dt02636a","url":null,"abstract":"The efficient and durable oxygen evolution reaction (OER) electrocatalysts are critical for enhancing proton exchange membrane water electrolyzer (PEMWE) performance. RuO2 has high intrinsic OER activity, but it is susceptible to oxidation into soluble RuO4− species in acidic electrolyte due to the highly reactive nature of lattice oxygen. Herein, we introduce an effective strategy aimed at bolstering structural stability by constructing Ru/RuO2 heterostructures onto carbon nanotubes (Ru/RuO2@CNT). The formation of Ru0−O−Ru4+ interfacial structures within these heterostructures effectively suppresses the Ru4+ oxidation state and simultaneously refines the d-band center of Ru sites for optimizing intermediates adsorption, thus accelerating the OER kinetics. Consequently, the Ru/RuO2@CNT-300 achieves a low overpotential of 169 mV at 10 mA cm−2 and displays remarkable durability exceeding 100 hours of stable operation in a 0.5 M H2SO4. The unique structure endows the Ru/RuO2@CNT-300 with exceptional acidic OER activity compared to most reported electrocatalysts. This work provides a feasible pathway for designing efficient and stable OER electrocatalysts for high-performance PEMWE.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"4 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145830022","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}
Chemodynamic therapy (CDT) is a tumor-specific treatment strategy that employs Fenton or Fenton-like reactions to convert endogenous hydrogen peroxide (H₂O₂) into highly cytotoxic hydroxyl radicals (·OH), thereby amplifying intracellular oxidative stress and inducing tumor cell apoptosis. However, its clinical translation is limited by insufficient endogenous H₂O₂ levels in tumors, suboptimal catalytic efficiency under the mildly acidic tumor microenvironment (TME), and glutathione (GSH)-mediated scavenging of reactive oxygen species (ROS). Addressing these challenges has led to strategic CDT enhancements centered on harnessing endogenous regulators in the TME, like pH, H₂O₂, and GSH. Moreover, CDT has been increasingly integrated with complementary treatment modalities, such as chemotherapy, sonodynamic therapy (SDT), photodynamic therapy (PDT), immunotherapy, and metabolic reprogramming, to achieve synergistic therapeutic outcomes. In this context, the rational design of metal complexes is crucial. Metal ions including Fe²⁺, Cu⁺, and Mn²⁺ play central roles in catalyzing Fenton or Fenton-like reactions. Recent advances in inorganic and coordination chemistry have enabled the design of metal complexes with improved catalytic activity, selectivity, and stability. Furthermore, the development of nanostructured materials, such as metal-organic frameworks (MOFs), porous nanocarriers, and heterojunction nanoparticles, has expanded the possibilities for combining CDT with other therapies. These nanostructures not only serve as efficient carriers for metal complexes but also offer additional functionalities, including targeted drug release, TME modulation, and ROS amplification. This review comprehensively summarizes recent progress in the field, with a focus on mechanistic insights, design principles, and emerging translational opportunities for CDT-based combination therapies.
{"title":"Recent Advances in Metal Complexes and Nanostructured Materials for Enhanced Chemodynamic Therapy","authors":"Wen-Ying Shen, Hong Liang, Zhen-Feng Chen","doi":"10.1039/d5dt02354h","DOIUrl":"https://doi.org/10.1039/d5dt02354h","url":null,"abstract":"Chemodynamic therapy (CDT) is a tumor-specific treatment strategy that employs Fenton or Fenton-like reactions to convert endogenous hydrogen peroxide (H₂O₂) into highly cytotoxic hydroxyl radicals (·OH), thereby amplifying intracellular oxidative stress and inducing tumor cell apoptosis. However, its clinical translation is limited by insufficient endogenous H₂O₂ levels in tumors, suboptimal catalytic efficiency under the mildly acidic tumor microenvironment (TME), and glutathione (GSH)-mediated scavenging of reactive oxygen species (ROS). Addressing these challenges has led to strategic CDT enhancements centered on harnessing endogenous regulators in the TME, like pH, H₂O₂, and GSH. Moreover, CDT has been increasingly integrated with complementary treatment modalities, such as chemotherapy, sonodynamic therapy (SDT), photodynamic therapy (PDT), immunotherapy, and metabolic reprogramming, to achieve synergistic therapeutic outcomes. In this context, the rational design of metal complexes is crucial. Metal ions including Fe²⁺, Cu⁺, and Mn²⁺ play central roles in catalyzing Fenton or Fenton-like reactions. Recent advances in inorganic and coordination chemistry have enabled the design of metal complexes with improved catalytic activity, selectivity, and stability. Furthermore, the development of nanostructured materials, such as metal-organic frameworks (MOFs), porous nanocarriers, and heterojunction nanoparticles, has expanded the possibilities for combining CDT with other therapies. These nanostructures not only serve as efficient carriers for metal complexes but also offer additional functionalities, including targeted drug release, TME modulation, and ROS amplification. This review comprehensively summarizes recent progress in the field, with a focus on mechanistic insights, design principles, and emerging translational opportunities for CDT-based combination therapies.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"18 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145830021","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}
Jonghyeon Lee, Gahyeon Baek, Youngjo Kim, Soyoung Park, Min Kim
Nucleobases are essential components of nucleic acids and provide multiple coordination sites, making them useful ligands for metal-based catalysis. Purine-type nucleobases such as adenine and guanine have been widely studied because of their rigid structures and strong metal-binding ability, whereas the pyrimidine-type cytosine (Cyt) has seen far less use in catalysis. Here, we present a new catalyst: a Cu-based metal–organic framework (MOF) modified with the biocompatible nucleobase Cyt. Silver ions are chelated by the Cyt-Ag structure inside the MOF, forming a bimetallic nanozyme named HKUST-1-Cyt-Ag (HKUST = Hong Kong University of Science and Technology). This hybrid exhibits strong laccase-like activity, driven by the synergy between the Cu-based HKUST-1 framework and the Cyt-Ag motif. To our knowledge, this is the first demonstration of ligand-chelating metalation in HKUST-1, highlighting its potential to mimic multicopper oxidase activity for biocatalytic applications.
{"title":"Cytosine–silver incorporated metal–organic framework for efficient laccase-mimicking reactions","authors":"Jonghyeon Lee, Gahyeon Baek, Youngjo Kim, Soyoung Park, Min Kim","doi":"10.1039/d5dt02837j","DOIUrl":"https://doi.org/10.1039/d5dt02837j","url":null,"abstract":"Nucleobases are essential components of nucleic acids and provide multiple coordination sites, making them useful ligands for metal-based catalysis. Purine-type nucleobases such as adenine and guanine have been widely studied because of their rigid structures and strong metal-binding ability, whereas the pyrimidine-type cytosine (Cyt) has seen far less use in catalysis. Here, we present a new catalyst: a Cu-based metal–organic framework (MOF) modified with the biocompatible nucleobase Cyt. Silver ions are chelated by the Cyt-Ag structure inside the MOF, forming a bimetallic nanozyme named HKUST-1-Cyt-Ag (HKUST = Hong Kong University of Science and Technology). This hybrid exhibits strong laccase-like activity, driven by the synergy between the Cu-based HKUST-1 framework and the Cyt-Ag motif. To our knowledge, this is the first demonstration of ligand-chelating metalation in HKUST-1, highlighting its potential to mimic multicopper oxidase activity for biocatalytic applications.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"33 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145830023","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}
Fe/Zn bimetallic co-doped layered manganese dioxide (FZMO) nanoflowers were synthesised using a one-step solvothermal method. The incorporation of iron and zinc cations stabilises the structure by generating oxygen vacancies, reducing the dimensions of the nanoflowers while increasing the interlayer spacing. This synergistic effect significantly enhances electrical conductivity and shortens ion migration pathways, thereby improving ion diffusion kinetics. Electrochemical tests showed that the FZMO cathode exhibited an improved capacity of 432.5 mAhg-1 at 0.2 Ag-1 and exhibited superior rate capability. Notably, it retained 90.16% of its capacity over 1000 cycles at a high current density of 1 A g-1, highlighting its exceptional stability.
采用一步溶剂热法合成了Fe/Zn双金属共掺杂层状二氧化锰（FZMO）纳米花。铁和锌阳离子的结合通过产生氧空位来稳定结构，减少了纳米花的尺寸，同时增加了层间间距。这种协同效应显著提高了电导率，缩短了离子迁移途径，从而改善了离子扩散动力学。电化学测试表明，在0.2 Ag-1条件下，FZMO阴极的容量提高到432.5 mAhg-1，并具有优越的倍率性能。值得注意的是，在1 a g-1的高电流密度下，它在1000次循环中保持了90.16%的容量，突出了其卓越的稳定性。
{"title":"Fe/Zn Co-doped MnO2 Nanoflowers for High-Performance Aqueous Zinc-Ion Batteries","authors":"Yannan Zhang, Jiawei Shi, Cheng Wang, Zhi-Yuan Yao, Yang Zou, Xiaoming Ren","doi":"10.1039/d5dt02713f","DOIUrl":"https://doi.org/10.1039/d5dt02713f","url":null,"abstract":"Fe/Zn bimetallic co-doped layered manganese dioxide (FZMO) nanoflowers were synthesised using a one-step solvothermal method. The incorporation of iron and zinc cations stabilises the structure by generating oxygen vacancies, reducing the dimensions of the nanoflowers while increasing the interlayer spacing. This synergistic effect significantly enhances electrical conductivity and shortens ion migration pathways, thereby improving ion diffusion kinetics. Electrochemical tests showed that the FZMO cathode exhibited an improved capacity of 432.5 mAhg-1 at 0.2 Ag-1 and exhibited superior rate capability. Notably, it retained 90.16% of its capacity over 1000 cycles at a high current density of 1 A g-1, highlighting its exceptional stability.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"2 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823674","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}
Michael Nivendran Pillay, Min-Chi Li, Yu-Rong Ni, Wei-Jung Yen, Tzu-Hao Chiu, Xiaoping Wang, Jean-Yves Saillard, Chen-Wei Liu
We report the first definitive neutron diffraction study aimed at resolving the P–OH/P=O structural ambiguity in metal dithiophosphonates. The small NH4 counterion forces a rare syn-configuration via an extended hydrogen-bonding network. Neutron analysis definitively confirmed the fully deprotonated P=O moiety, thus confirming the formation of a dianionic dithiophosphonate, a versatile synthon in homoleptic and heteroleptic coordination environments.
{"title":"Solving the P-O/P-OH Riddle: Direct Synthesis and Neutron Diffraction Characterization of Dianionic Dithiophosphonates","authors":"Michael Nivendran Pillay, Min-Chi Li, Yu-Rong Ni, Wei-Jung Yen, Tzu-Hao Chiu, Xiaoping Wang, Jean-Yves Saillard, Chen-Wei Liu","doi":"10.1039/d5dt02816g","DOIUrl":"https://doi.org/10.1039/d5dt02816g","url":null,"abstract":"We report the first definitive neutron diffraction study aimed at resolving the P–OH/P=O structural ambiguity in metal dithiophosphonates. The small NH4 counterion forces a rare syn-configuration via an extended hydrogen-bonding network. Neutron analysis definitively confirmed the fully deprotonated P=O moiety, thus confirming the formation of a dianionic dithiophosphonate, a versatile synthon in homoleptic and heteroleptic coordination environments.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813177","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}
Reactions of AuCl(PR3) with NaOC(CF3)3 in the presence of 1 equiv. of Ag[BF4] or Ag[PF6] afforded the gold(I) alkoxide complexes [(Au{OC(CF3)3}{PR3})n] (R = Me (1), Et (2), iPr (3) and tBu (4)). In our hands, analogous reactions using NaOtBu (for R = iPr) did not yield a thermally robust product. However, the thiolate complexes [{Au(StBu)(PR3)}n] (R = Me (5) and iPr (6)) were accessed by reaction of [{Au(StBu)}n] with PR3. Compound 1 is a trimer featuring linear Au{OC(CF3)3}(PMe3) units connected through unsupported aurophilic interactions, whereas more sterically hindered 3 and 4 are monomers in the solid state. Compound 5 is a dimer connected via an aurophilic interaction, while 6 is a monomer. In solution, 1 and 3 reacted almost instantly with HBpin or H3SiPh to afford metallic gold and volatile byproducts (free PR3 and H2 accompanied by {(F3C)3CO}Bpin or a mixture of {(F3C)3CO}SiH2Ph and {(F3C)3CO}2SiHPh). By contrast, analogous reactions with thiolate complex 5 required over 24 hours to reach completion. Complexes 1-4 melted at 105-106, 19-21, 59-61 and 181-183 °C, respectively, and sublimed cleanly between 50 and 80 °C at 5 mTorr. By contrast, 5-6 decomposed (completely or partially) during attempted sublimation at 5 mTorr; in the case of 5, decomposition was shown to occur via phosphine dissociation to re-form [{Au(StBu)}n]. Of the complexes in this work, 3 offers the best combination of thermal stability and volatility, and the relatively low melting point is attractive. However, 3 was ∼4% decomposed after 72 h at 85 °C, and ∼10% decomposed after 96 h at 100 °C, forming soluble [Au(PiPr3)2][H{OC(CF3)3}2] (7), gold metal, and other insoluble product(s). Preliminary ALD reactor experiments using 3 (with a delivery temperature of 85 °C) and HBpin showed gold deposition at 124 °C, and no deposition was observed at this temperature using 3 without HBpin.
{"title":"Gold(I) alkoxide and thiolate complexes as potential atomic layer deposition precursors.","authors":"Nicholas A Hoffman,David J H Emslie","doi":"10.1039/d5dt02836a","DOIUrl":"https://doi.org/10.1039/d5dt02836a","url":null,"abstract":"Reactions of AuCl(PR3) with NaOC(CF3)3 in the presence of 1 equiv. of Ag[BF4] or Ag[PF6] afforded the gold(I) alkoxide complexes [(Au{OC(CF3)3}{PR3})n] (R = Me (1), Et (2), iPr (3) and tBu (4)). In our hands, analogous reactions using NaOtBu (for R = iPr) did not yield a thermally robust product. However, the thiolate complexes [{Au(StBu)(PR3)}n] (R = Me (5) and iPr (6)) were accessed by reaction of [{Au(StBu)}n] with PR3. Compound 1 is a trimer featuring linear Au{OC(CF3)3}(PMe3) units connected through unsupported aurophilic interactions, whereas more sterically hindered 3 and 4 are monomers in the solid state. Compound 5 is a dimer connected via an aurophilic interaction, while 6 is a monomer. In solution, 1 and 3 reacted almost instantly with HBpin or H3SiPh to afford metallic gold and volatile byproducts (free PR3 and H2 accompanied by {(F3C)3CO}Bpin or a mixture of {(F3C)3CO}SiH2Ph and {(F3C)3CO}2SiHPh). By contrast, analogous reactions with thiolate complex 5 required over 24 hours to reach completion. Complexes 1-4 melted at 105-106, 19-21, 59-61 and 181-183 °C, respectively, and sublimed cleanly between 50 and 80 °C at 5 mTorr. By contrast, 5-6 decomposed (completely or partially) during attempted sublimation at 5 mTorr; in the case of 5, decomposition was shown to occur via phosphine dissociation to re-form [{Au(StBu)}n]. Of the complexes in this work, 3 offers the best combination of thermal stability and volatility, and the relatively low melting point is attractive. However, 3 was ∼4% decomposed after 72 h at 85 °C, and ∼10% decomposed after 96 h at 100 °C, forming soluble [Au(PiPr3)2][H{OC(CF3)3}2] (7), gold metal, and other insoluble product(s). Preliminary ALD reactor experiments using 3 (with a delivery temperature of 85 °C) and HBpin showed gold deposition at 124 °C, and no deposition was observed at this temperature using 3 without HBpin.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"12 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807893","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}
Jie Chen, Hao Qu, Jie Zhang, Meng-Rui Huo, Wen-Wen Zhang, Bing-Qi Liu, Jianfei Chai, Chunqing Ji, Xiangyu Chen, Yuyin Wang, Yan Zhou, Guoming Lin
Zero-dimensional (0D) organic-inorganic hybrid halides have emerged as promising luminescent materials, but their poor environmental stability has limited practical applications. Here we report centimeter-sized single crystals of [MAPPA]CdBr 4 •H 2 O (MAPPA = protonated 1-methyl-4-(6-aminopyridin-3-yl)piperazine), which exhibit blue emission with a photoluminescence quantum yield of 46.7%. The emission is excitation-wavelength-independent, stable across different excitation powers, and governed by a temperature-driven balance between thermally activated blue emission and self-trapped exciton-mediated yellow emission. Time-resolved spectroscopy reveals moderate thermal quenching, while density functional theory calculations indicate that the emission originates from Br-4p → Cd-5s/Br-4p transitions, facilitated by a Jahn-Teller distortion of the [CdBr 4 ] 2-tetrahedron. [MAPPA]CdBr 4 •H 2 O retains both luminescence and crystallographic integrity after extended exposure to water (50 days) and air (150 days), demonstrating notable environmental resilience. When integrated into a white light-emitting diode (WLED) with commercial phosphors, the material yields warm-white emission with a high color rendering index (91) and stable chromaticity across operating currents. These findings highlight [MAPPA]CdBr 4 •H 2 O as a robust 0D halide hybrid, offering valuable design insights for developing environmentally stable blue emitters for next-generation solid-state lighting.
{"title":"A centimeter-sized water-resistant blue-light-emitting zero-dimensional hybrid halide for solid-state lighting","authors":"Jie Chen, Hao Qu, Jie Zhang, Meng-Rui Huo, Wen-Wen Zhang, Bing-Qi Liu, Jianfei Chai, Chunqing Ji, Xiangyu Chen, Yuyin Wang, Yan Zhou, Guoming Lin","doi":"10.1039/d5dt02670a","DOIUrl":"https://doi.org/10.1039/d5dt02670a","url":null,"abstract":"Zero-dimensional (0D) organic-inorganic hybrid halides have emerged as promising luminescent materials, but their poor environmental stability has limited practical applications. Here we report centimeter-sized single crystals of [MAPPA]CdBr 4 •H 2 O (MAPPA = protonated 1-methyl-4-(6-aminopyridin-3-yl)piperazine), which exhibit blue emission with a photoluminescence quantum yield of 46.7%. The emission is excitation-wavelength-independent, stable across different excitation powers, and governed by a temperature-driven balance between thermally activated blue emission and self-trapped exciton-mediated yellow emission. Time-resolved spectroscopy reveals moderate thermal quenching, while density functional theory calculations indicate that the emission originates from Br-4p → Cd-5s/Br-4p transitions, facilitated by a Jahn-Teller distortion of the [CdBr 4 ] 2-tetrahedron. [MAPPA]CdBr 4 •H 2 O retains both luminescence and crystallographic integrity after extended exposure to water (50 days) and air (150 days), demonstrating notable environmental resilience. When integrated into a white light-emitting diode (WLED) with commercial phosphors, the material yields warm-white emission with a high color rendering index (91) and stable chromaticity across operating currents. These findings highlight [MAPPA]CdBr 4 •H 2 O as a robust 0D halide hybrid, offering valuable design insights for developing environmentally stable blue emitters for next-generation solid-state lighting.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813583","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}
Chennuo Jiang, Lianyu Chen, Yujie Jin, Jiyong Liu, Kang Zhang, Simon Duttwyler
A series of highly stable iodonium salts [I(4-RPy)2][CB11H6X6] (R= H, NMe2, OMe, Me, NO2; X= Cl, Br, I) were isolated and characterized. These salts exhibit excellent solid-state stability and serve as efficient electrophilic iodinating reagents, enabling selective iodination at the B12 position of monocarborane anion [CB11H12]-.
{"title":"Monocarborane-stabilized iodonium salts enable regioselective B12-iodination of [CB11H12]⁻","authors":"Chennuo Jiang, Lianyu Chen, Yujie Jin, Jiyong Liu, Kang Zhang, Simon Duttwyler","doi":"10.1039/d5dt02721g","DOIUrl":"https://doi.org/10.1039/d5dt02721g","url":null,"abstract":"A series of highly stable iodonium salts [I(4-RPy)2][CB11H6X6] (R= H, NMe2, OMe, Me, NO2; X= Cl, Br, I) were isolated and characterized. These salts exhibit excellent solid-state stability and serve as efficient electrophilic iodinating reagents, enabling selective iodination at the B12 position of monocarborane anion [CB11H12]-.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813585","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}
Thin film solid-state electrolytes (SSEs) have emerged as a key component in the development of microenergy storage devices, offering improved safety, stability and compatibility with advanced electrode materials. Among these electrolytes, lithium phosphorus oxynitride (LiPON) stands out as a relevant SSE candidate for microsupercapacitor applications. As with most ionic conductors, a margin for improvement always exists to enhance their overall performance. Within this scope, efforts to optimize LiPON through doping have been extensively explored, primarily using Physical Vapour Deposition (PVD) to provide films with relatively high thicknesses (500 nm-1 µm) and superior ionic conductivity. In this study, the use of Atomic Layer Deposition (ALD) for doping LiPON thin films (<50 nm) was explored for the first time, by inserting aluminum oxide (Al2O3) as a network former. Through the ALD supercycle approach, Al2O3 doped-LiPON thin films were deposited at 330 °C, using lithium hexamethyldisilazide (LiHMDS) and diethyl phosphoramidate (DEPA), while Al2O3 traces were injected during the film growth via trimethylaluminum (TMA) and water (H2O) pulses. The resulting amorphous films were depth profiled by Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and demonstrated a uniform distribution of aluminium throughout the film's thickness for different doping levels. The incorporation of Al2O3 is intended to enable additional Li+ transport pathways through modified bridging configurations, particularly in oxygen and nitrogen environments. The Fourier transform infrared spectroscopy (FTIR) analysis indicated a prevalence of Bridging Oxygen (BO) and divalent nitrogen (Nd) units upon doping. These findings were further supported by X-ray photoelectron spectroscopy (XPS), underlining an increase in the ratios of Bridging Oxygen to Non-Bridging Oxygen (BO/NBO) and divalent nitrogen to trivalent nitrogen (Nd/Nt) along with higher lithium and lower carbon concentrations. The obtained structural modifications were accompanied by a stimulated Li+ ionic transport and a reduced activation energy, while maintaining a good insulating property and an electrochemical stability over a wide voltage window (up to 6 V).
{"title":"Unveiling the structural and electrochemical effects of Al2O3 incorporation within LiPON electrolyte thin films by atomic layer deposition.","authors":"Ilyass Ghandari,Nicolas Gauthier,Névine Rochat,Sylvain Poulet,Lara Casiez,Manon Letiche,Violaine Salvador,Hélène Coudert-Alteirac,Nicolas Vaxelaire,Mikhael Bechelany,Messaoud Bedjaoui","doi":"10.1039/d5dt02597d","DOIUrl":"https://doi.org/10.1039/d5dt02597d","url":null,"abstract":"Thin film solid-state electrolytes (SSEs) have emerged as a key component in the development of microenergy storage devices, offering improved safety, stability and compatibility with advanced electrode materials. Among these electrolytes, lithium phosphorus oxynitride (LiPON) stands out as a relevant SSE candidate for microsupercapacitor applications. As with most ionic conductors, a margin for improvement always exists to enhance their overall performance. Within this scope, efforts to optimize LiPON through doping have been extensively explored, primarily using Physical Vapour Deposition (PVD) to provide films with relatively high thicknesses (500 nm-1 µm) and superior ionic conductivity. In this study, the use of Atomic Layer Deposition (ALD) for doping LiPON thin films (<50 nm) was explored for the first time, by inserting aluminum oxide (Al2O3) as a network former. Through the ALD supercycle approach, Al2O3 doped-LiPON thin films were deposited at 330 °C, using lithium hexamethyldisilazide (LiHMDS) and diethyl phosphoramidate (DEPA), while Al2O3 traces were injected during the film growth via trimethylaluminum (TMA) and water (H2O) pulses. The resulting amorphous films were depth profiled by Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and demonstrated a uniform distribution of aluminium throughout the film's thickness for different doping levels. The incorporation of Al2O3 is intended to enable additional Li+ transport pathways through modified bridging configurations, particularly in oxygen and nitrogen environments. The Fourier transform infrared spectroscopy (FTIR) analysis indicated a prevalence of Bridging Oxygen (BO) and divalent nitrogen (Nd) units upon doping. These findings were further supported by X-ray photoelectron spectroscopy (XPS), underlining an increase in the ratios of Bridging Oxygen to Non-Bridging Oxygen (BO/NBO) and divalent nitrogen to trivalent nitrogen (Nd/Nt) along with higher lithium and lower carbon concentrations. The obtained structural modifications were accompanied by a stimulated Li+ ionic transport and a reduced activation energy, while maintaining a good insulating property and an electrochemical stability over a wide voltage window (up to 6 V).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"24 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145807894","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：