Herein, the exploring advanced materials in the highly effective removal of uranium is highly desired. Three amidoxime-functionalized conjugated microporous polymer (CMP-AO) networks with different architectures were synthesized by Sonogashira-Hagihara coupling reaction. The effect of various factors on the photoreduction of U(VI) on CMP-AO was systemically investigated. The fast photocatalytic efficiency (K1 = 0.00713 /min), superior selectivity and prominent recyclability of U(VI) on CMPs1-AO was achieved due to the outstanding separation of photogenerated carriers, good chemical stability, massive functional groups. According to trapping and EPR analysis, the photogenerated electrons and superoxide radicals played an important role in U(VI) photoreduction. The introduction of AO groups was favorable for the photoreduction of U(VI) into U(VI) by XPS analysis. These findings are crucial for the rational design of CMPs in removing U(VI) from aqueous solution.
{"title":"Constructing crosslinked architecture in conjugated microporous polymers for highly efficient uranium (VI) photoreduction","authors":"Guangyu Xu, Qi Chen, Caijuan lu, Luxin Huang, Zhengfeng Hu, Muqing Qiu","doi":"10.1039/d5dt02520f","DOIUrl":"https://doi.org/10.1039/d5dt02520f","url":null,"abstract":"Herein, the exploring advanced materials in the highly effective removal of uranium is highly desired. Three amidoxime-functionalized conjugated microporous polymer (CMP-AO) networks with different architectures were synthesized by Sonogashira-Hagihara coupling reaction. The effect of various factors on the photoreduction of U(VI) on CMP-AO was systemically investigated. The fast photocatalytic efficiency (K1 = 0.00713 /min), superior selectivity and prominent recyclability of U(VI) on CMPs1-AO was achieved due to the outstanding separation of photogenerated carriers, good chemical stability, massive functional groups. According to trapping and EPR analysis, the photogenerated electrons and superoxide radicals played an important role in U(VI) photoreduction. The introduction of AO groups was favorable for the photoreduction of U(VI) into U(VI) by XPS analysis. These findings are crucial for the rational design of CMPs in removing U(VI) from aqueous solution.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"118 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145665223","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}
Giulia Ferrari, Ines Lopez-Martinez, Mohamed Saqawa, Eithne Dempsey, Thomas Wanek, Irena Pashkunova-Martic, Silvia Panseri, Marcus Hacker, Monica Montesi, Claudia Kuntner, Diego Montagner
Since the discovery of cisplatin’s anticancer activity and its clinical approval in 1978, substantial efforts have focused on improving its physiological stability and minimizing off-target toxicity. One promising strategy has been the development of Pt(IV) complexes, which act as redox-activated prodrugs with improved pharmacological profiles compared to Pt(II) drugs. In this study, we present the synthesis of three novel Pt(IV) complexes bearing a pendant deferoxamine (DFO) chelator, designed for theranostic application, combining therapeutic activity with radiometal labeling for positron emission tomography (PET) imaging. Platinum-based drugs are still the gold standard therapy for osteosarcoma but the limited utility and the resistance mechanisms indicate an urgent need for new approaches. In vitro studies demonstrated that these complexes are efficiently internalized by osteosarcoma cells and exhibit minimal toxicity toward healthy MDCK.2 kidney cells, indicating a favorable safety profile. Radiolabeling with Gallium-68 was achieved under mild conditions, yielding stable radiotracers in various biological media after 1h incubation. This study represents one of the first demonstrations of Pt(IV) theranostic agents suitable for PET imaging, enabling future investigations of Pt(IV) biodistribution profiles that go beyond traditional therapeutic evaluations.
{"title":"68Ga Radiolabeling strategies in Pt(IV)-deferoxamine scaffolds for potential theranostic application","authors":"Giulia Ferrari, Ines Lopez-Martinez, Mohamed Saqawa, Eithne Dempsey, Thomas Wanek, Irena Pashkunova-Martic, Silvia Panseri, Marcus Hacker, Monica Montesi, Claudia Kuntner, Diego Montagner","doi":"10.1039/d5dt02352a","DOIUrl":"https://doi.org/10.1039/d5dt02352a","url":null,"abstract":"Since the discovery of cisplatin’s anticancer activity and its clinical approval in 1978, substantial efforts have focused on improving its physiological stability and minimizing off-target toxicity. One promising strategy has been the development of Pt(IV) complexes, which act as redox-activated prodrugs with improved pharmacological profiles compared to Pt(II) drugs. In this study, we present the synthesis of three novel Pt(IV) complexes bearing a pendant deferoxamine (DFO) chelator, designed for theranostic application, combining therapeutic activity with radiometal labeling for positron emission tomography (PET) imaging. Platinum-based drugs are still the gold standard therapy for osteosarcoma but the limited utility and the resistance mechanisms indicate an urgent need for new approaches. In vitro studies demonstrated that these complexes are efficiently internalized by osteosarcoma cells and exhibit minimal toxicity toward healthy MDCK.2 kidney cells, indicating a favorable safety profile. Radiolabeling with Gallium-68 was achieved under mild conditions, yielding stable radiotracers in various biological media after 1h incubation. This study represents one of the first demonstrations of Pt(IV) theranostic agents suitable for PET imaging, enabling future investigations of Pt(IV) biodistribution profiles that go beyond traditional therapeutic evaluations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"21 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145650935","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}
Yanyang Li, Lu Lei, Sirui Shu, Jian Zou, Shanshan Hu, Jun Yang
Sb3+ doped inorganic perov-skites have attracted great attention for anti-counterfeiting and infor-mation encryption applica-tions due to their excellent optical properties. We have synthesized a novel perov-skite Cs2KLuCl6, which ex-hibits weak cyan emission originating from the self-trapped excitons (STEs) of the host. Its photolumines-cence quantum yield is enhanced from 2% to 68% by Sb3+ doping. The energy transfer channel from STEs to Ho3+ was constructed, and the luminescence color was modulated from cyan to white with the increase of Ho3+ doping concentra-tion. The Sb3+/Ho3+ co-doped sample has two-color luminescence performance due to the introduction of new emission centers. Up-conversion green emission was obtained by introduc-ing Yb3+/Er3+. Finally, the optical properties of the obtained samples were utilized to design an anti-counterfeit label and in-formation encryption strategy.
{"title":"Multicolor lu-minescence of Cs2KLuCl6 for an-ti-counterfeiting and information encryption ap-plications","authors":"Yanyang Li, Lu Lei, Sirui Shu, Jian Zou, Shanshan Hu, Jun Yang","doi":"10.1039/d5dt02031j","DOIUrl":"https://doi.org/10.1039/d5dt02031j","url":null,"abstract":"Sb3+ doped inorganic perov-skites have attracted great attention for anti-counterfeiting and infor-mation encryption applica-tions due to their excellent optical properties. We have synthesized a novel perov-skite Cs2KLuCl6, which ex-hibits weak cyan emission originating from the self-trapped excitons (STEs) of the host. Its photolumines-cence quantum yield is enhanced from 2% to 68% by Sb3+ doping. The energy transfer channel from STEs to Ho3+ was constructed, and the luminescence color was modulated from cyan to white with the increase of Ho3+ doping concentra-tion. The Sb3+/Ho3+ co-doped sample has two-color luminescence performance due to the introduction of new emission centers. Up-conversion green emission was obtained by introduc-ing Yb3+/Er3+. Finally, the optical properties of the obtained samples were utilized to design an anti-counterfeit label and in-formation encryption strategy.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"198200 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613918","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}
Zero-dimension (0D) zinc halides have attracted intensive attention in multiple optoelectronic fields due to their excellent stability. However, most Zn-based halides show relatively weak luminescence efficiency, which limits their further widespread applications. Herein, we successfully optimized the electronic structure of a new 0D Zn halide [MTPP]2ZnBr4 ([MTPP]Br = Methyltriphenylphosphonium bromide) by Cu+ doping strategy to realize highly efficient and adjustable dual-color emission. Compared with weak blue-green emission of undoped [MTPP]2ZnBr4, the incorporating of Cu+ ion results in a newly emerged intense orange emission at 630 nm with highest photoluminescence quantum yield (PLQY) of 39.17%. More significantly, the relative intensities of dual emission feature transformation depending on environment temperature due to thermally associated reversible energy transfer between each self-trapped excitonic (STE) state, which enables this doped phase to act as a promising luminescent ratiometric thermometer with relative thermal sensitivity of 0.94% K-1 in the range of 80-260 K. Furthermore, this phenomenon also enables the material to achieve tunable multicolor luminescence with advanced applications in anti-counterfeiting. This study not only realizes highly efficient dual-color emissions in Zn-based halide, but also achieves temperature-dependent thermochromism luminescence with wide applications in temperature monitoring and anti-counterfeiting.
{"title":"A Cu+-Doped Zinc Organic Halide with Temperature-Dependent Dual-color Emission as Thermochromic Molecular Thermometer","authors":"Yu-Fang Wu, Ya-Hui Li, Zhi-Meng Sui, Yu-Kun Wei, Rui-Han Wei, Xiao Chen, Xiao-Hua Yang, Zhi-Wei Chen, Zhihong Jing, Cheng-Yang Yue","doi":"10.1039/d5dt02474a","DOIUrl":"https://doi.org/10.1039/d5dt02474a","url":null,"abstract":"Zero-dimension (0D) zinc halides have attracted intensive attention in multiple optoelectronic fields due to their excellent stability. However, most Zn-based halides show relatively weak luminescence efficiency, which limits their further widespread applications. Herein, we successfully optimized the electronic structure of a new 0D Zn halide [MTPP]2ZnBr4 ([MTPP]Br = Methyltriphenylphosphonium bromide) by Cu+ doping strategy to realize highly efficient and adjustable dual-color emission. Compared with weak blue-green emission of undoped [MTPP]2ZnBr4, the incorporating of Cu+ ion results in a newly emerged intense orange emission at 630 nm with highest photoluminescence quantum yield (PLQY) of 39.17%. More significantly, the relative intensities of dual emission feature transformation depending on environment temperature due to thermally associated reversible energy transfer between each self-trapped excitonic (STE) state, which enables this doped phase to act as a promising luminescent ratiometric thermometer with relative thermal sensitivity of 0.94% K-1 in the range of 80-260 K. Furthermore, this phenomenon also enables the material to achieve tunable multicolor luminescence with advanced applications in anti-counterfeiting. This study not only realizes highly efficient dual-color emissions in Zn-based halide, but also achieves temperature-dependent thermochromism luminescence with wide applications in temperature monitoring and anti-counterfeiting.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613919","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}
Vacancies in catalysts are known to critically influence catalytic activity, yet metal vacancies—especially non-interfacial metal vacancies—remain underexplored due to their intrinsically high formation energies and synthetic challenges. In this work, we successfully prepared a Ni2.8S2 precursor containing nickel vacancies through a high-temperature solid-state reaction, which was subsequently transformed in situ into a NiS/NiSe2 heterostructure featuring dual non-interfacial metal vacancies. Notably, these vacancy characteristics were preserved during the phase transition, yielding a robust NiS/NiSe2 heterointerface with enhanced charge transfer and strengthened interphase coupling. Compared with a vacancy-free NiS/NiSe2 counterpart, the vacancy-enriched heterostructure exhibits markedly improved hydrogen evolution activity. Density functional theory (DFT) calculations further reveal that the dual non-interfacial vacancies induce a downward shift in the Ni d-band center, which plays a pivotal role in boosting catalytic performance. This study underscores the importance of non-interfacial metal vacancies in designing high-performance electrocatalysts for hydrogen evolution and offers valuable insights for developing efficient, low-cost, and non-precious metal-based catalysts.
{"title":"Formation of Ni2.8S2-based heterojunction with dual non-interfacial metal vacancies for enhanced hydrogen evolution performance","authors":"Zongpeng Wang, Longfei Ding, Xiang Li, Yuanmo Lin, Ting Jiang, Zhiping Lin, Shougang Chen","doi":"10.1039/d5dt02557e","DOIUrl":"https://doi.org/10.1039/d5dt02557e","url":null,"abstract":"Vacancies in catalysts are known to critically influence catalytic activity, yet metal vacancies—especially non-interfacial metal vacancies—remain underexplored due to their intrinsically high formation energies and synthetic challenges. In this work, we successfully prepared a Ni2.8S2 precursor containing nickel vacancies through a high-temperature solid-state reaction, which was subsequently transformed in situ into a NiS/NiSe2 heterostructure featuring dual non-interfacial metal vacancies. Notably, these vacancy characteristics were preserved during the phase transition, yielding a robust NiS/NiSe2 heterointerface with enhanced charge transfer and strengthened interphase coupling. Compared with a vacancy-free NiS/NiSe2 counterpart, the vacancy-enriched heterostructure exhibits markedly improved hydrogen evolution activity. Density functional theory (DFT) calculations further reveal that the dual non-interfacial vacancies induce a downward shift in the Ni d-band center, which plays a pivotal role in boosting catalytic performance. This study underscores the importance of non-interfacial metal vacancies in designing high-performance electrocatalysts for hydrogen evolution and offers valuable insights for developing efficient, low-cost, and non-precious metal-based catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"172 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613923","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}
Two-dimensional (2D) layered double hydroxides (LDHs) as an embryonic class of advanced energy materials hold great promise in sustainable electrocatalysis and renewable energy technology. LDHs offer abundant active sites, tuneable functionality, multi-faceted morphology and robust framework structure. This review entails a concise summary of the promising synthetic strategies and functional design for in situ transformation of metal-organic frameworks (MOFs) into 2D LDH electrocatalysts.We further discuss the description and role of commonly employed in situ/operando characterisation techniques, such as Raman spectroscopy, Attenuated Total Reflectance Fourier-transform infrared (ATR-FTIR), Electrochemical Impedance Spectroscopy (EIS), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and liquid-cell transmission electron microscopy (LCTEM), for unravelling the dynamic mechanisms and phases during electrocatalytic oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) in alkaline water splitting. Finally, this work marks the prevailing challenges in the current 2D LDH research and offers guidance for the future design of advanced 2D LDH energy materials with desired functionality for sustainable energy solutions.
{"title":"Tracking In Situ Transformation of Metal-Organic Frameworks into Layered Double Hydroxides During Synthesis and Alkaline Water Oxidation through Operando Mechanistic Studies","authors":"Meena Chettri, Nilankar Diyali, Bhaskar Biswas","doi":"10.1039/d5dt01557j","DOIUrl":"https://doi.org/10.1039/d5dt01557j","url":null,"abstract":"Two-dimensional (2D) layered double hydroxides (LDHs) as an embryonic class of advanced energy materials hold great promise in sustainable electrocatalysis and renewable energy technology. LDHs offer abundant active sites, tuneable functionality, multi-faceted morphology and robust framework structure. This review entails a concise summary of the promising synthetic strategies and functional design for in situ transformation of metal-organic frameworks (MOFs) into 2D LDH electrocatalysts.We further discuss the description and role of commonly employed in situ/operando characterisation techniques, such as Raman spectroscopy, Attenuated Total Reflectance Fourier-transform infrared (ATR-FTIR), Electrochemical Impedance Spectroscopy (EIS), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and liquid-cell transmission electron microscopy (LCTEM), for unravelling the dynamic mechanisms and phases during electrocatalytic oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) in alkaline water splitting. Finally, this work marks the prevailing challenges in the current 2D LDH research and offers guidance for the future design of advanced 2D LDH energy materials with desired functionality for sustainable energy solutions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"1 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145613920","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}
Ligand field theory (LFT) is generally formulated either as an application of the linear combination of atomic orbitals (LCAO) molecular orbital (MO) model (LFT-MO) or freely-parameterised crystal field theory with the 'global' crystal field replaced by the 'local' cellular ligand field (CLF) formalism (LFT-CLF). LFT-MO and LFT-CLF are conceptually and numerically different. These differences are highlighted by the LFT-MO concept of an 'inverted ligand field' (ILF). Using formally low-spin d8 and d7 ML 4 complexes, it is demonstrated that the LFT-MO ILF concept does not account for how the structures and reactivities of these systems change as a function of L or formal metal oxidation state.The LFT-MO overlap picture is an inadequate representation of how the sub-shell d electrons in transition metal complexes actually interact with their surroundings. The LFT-CLF picture of d electrons localised on the metal, but sensitive to the topology of the ligand field potential, VLF , is a better model. However, VLF does not invert. Instead, the 'internal redox' chemistry that the ILF concept attempts to rationalise is described via the LFT-CLF d-level breach. Conceptually, a d-level breach occurs when the bonding levels get too high or the d levels get too low. The empty d levels are filled and the integrity of the original dn configuration is compromised. A d-level breach should be abrupt with a significant impact on the geometric and electronic structure. This behaviour is confirmed computationally. The d-level breach is a significant descriptor for predicting enhanced ligand electrophilicity while the absence of a breach unambiguously and definitively confirms the dn configuration and metal oxidation state. In contrast, the %d components of canonical LCAO-type MOs used to invoke an ILF are unreliable descriptors and cannot be used to assign oxidation states. In general, ILFs have little chemical relevance but they are important here since they highlight several conceptual and numerical deficiencies of the theory which has underpinned the LFT-MO picture of TM systems for over 60 years.
配体场理论（LFT）通常表述为原子轨道线性组合（LCAO）分子轨道（MO）模型（LFT-MO）或自由参数化晶体场理论的应用，其中“全局”晶体场被“局部”细胞配体场（CLF）形式主义（LFT-CLF）所取代。LFT-MO和LFT-CLF在概念和数值上是不同的。LFT-MO的“反向配体场”（ILF）概念突出了这些差异。使用形式低自旋d8和d7 ML - 4配合物，证明了LFT-MO ILF概念不能解释这些体系的结构和反应性如何随着L或形式金属氧化态的变化而变化。LFT-MO重叠图不足以表示过渡金属配合物中的亚壳层d电子实际上是如何与周围环境相互作用的。LFT-CLF图像的d电子定位在金属上，但对配体场电位的拓扑结构敏感，是一个更好的模型。然而，VLF不会反转。相反，ILF概念试图合理化的“内部氧化还原”化学是通过LFT-CLF的d水平突破来描述的。从概念上讲，当成键水平过高或d水平过低时，就会发生d能级断裂。空的d级别将被填充，原始dn配置的完整性将受到损害。d级缺口应该是突然的，对几何和电子结构有重大影响。这种行为在计算上得到了证实。d级裂口是预测配体亲电性增强的重要描述符，而没有裂口则明确地证实了dn构型和金属氧化态。相反，用于调用ILF的典型lcao型MOs的%d组分是不可靠的描述符，不能用于指定氧化态。一般来说，ilf几乎没有化学相关性，但它们在这里很重要，因为它们突出了理论的几个概念和数值缺陷，这些缺陷支撑了60多年来TM系统的LFT-MO图像。
{"title":"Inverted Ligand Fields: A Conceptual Dilemma for Molecular Orbital Theory","authors":"Robert J. Deeth","doi":"10.1039/d5dt02371h","DOIUrl":"https://doi.org/10.1039/d5dt02371h","url":null,"abstract":"Ligand field theory (LFT) is generally formulated either as an application of the linear combination of atomic orbitals (LCAO) molecular orbital (MO) model (LFT-MO) or freely-parameterised crystal field theory with the 'global' crystal field replaced by the 'local' cellular ligand field (CLF) formalism (LFT-CLF). LFT-MO and LFT-CLF are conceptually and numerically different. These differences are highlighted by the LFT-MO concept of an 'inverted ligand field' (ILF). Using formally low-spin d<small><sup>8</sup></small> and d<small><sup>7</sup></small> ML<small><sub> 4</sub></small> complexes, it is demonstrated that the LFT-MO ILF concept does not account for how the structures and reactivities of these systems change as a function of L or formal metal oxidation state.The LFT-MO overlap picture is an inadequate representation of how the sub-shell d electrons in transition metal complexes actually interact with their surroundings. The LFT-CLF picture of d electrons localised on the metal, but sensitive to the topology of the ligand field potential, V<small><sub>LF</sub></small> , is a better model. However, V<small><sub>LF</sub></small> does not invert. Instead, the 'internal redox' chemistry that the ILF concept attempts to rationalise is described via the LFT-CLF d-level breach. Conceptually, a d-level breach occurs when the bonding levels get too high or the d levels get too low. The empty d levels are filled and the integrity of the original d<small><sup>n</sup></small> configuration is compromised. A d-level breach should be abrupt with a significant impact on the geometric and electronic structure. This behaviour is confirmed computationally. The d-level breach is a significant descriptor for predicting enhanced ligand electrophilicity while the absence of a breach unambiguously and definitively confirms the d<small><sup>n</sup></small> configuration and metal oxidation state. In contrast, the %d components of canonical LCAO-type MOs used to invoke an ILF are unreliable descriptors and cannot be used to assign oxidation states. In general, ILFs have little chemical relevance but they are important here since they highlight several conceptual and numerical deficiencies of the theory which has underpinned the LFT-MO picture of TM systems for over 60 years.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"147 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145612015","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}
Junli Xu, Yujiao Li, Zhaoshun Liu, Zhongning Shi, Hongbin Sun
Sulfur doping is an effective strategy to improve the rate capability and capacitance of nickelcobalt layered double hydroxide (NiCo-LDH). However, it causes a decrease in cycling stability due to the leaching of S, which further results in the dissolution of metal sites and damage of structure. In this study, only internal sulfur doped NiCo-LDH was constructed via a two-step electrodeposition method. The results show that the S doped core can enhance the materials electronic conductivity, while the pristine NiCo-LDH shell can restrict the migration of sulfur atoms from internal to interfacial, lowering sulfur and metal element dissolution losses.Moreover, the only internal S-doped NiCo-LDH structure creates a favorable interface for efficient charge transfer. These merits lead to a high specific capacitance and rate capability, as well as good cycling stability of internal S-doped NiCo-LDH. The specific capacitance is as high as 1453.42 F g -1 , and the capacitance retention rate is 82.8% after 2000 cycles. This study provides new insights into the rational structure design of high-performance LDHs with both high energy density and long lifespan.
硫掺杂是提高镍钴层状双氢氧化物（NiCo-LDH）倍率性能和电容的有效策略。但由于S的浸出导致循环稳定性降低，进一步导致金属位点的溶解和结构的破坏。在本研究中，仅通过两步电沉积法构建了内硫掺杂的NiCo-LDH。结果表明，S掺杂的核心可以提高材料的电子导电性，而原始的NiCo-LDH壳层可以限制硫原子从内部向界面的迁移，降低硫和金属元素的溶解损失。此外，唯一的内部s掺杂NiCo-LDH结构为有效的电荷转移创造了有利的界面。这些优点使得内掺s的NiCo-LDH具有较高的比电容和倍率能力，以及良好的循环稳定性。比电容高达1453.42 F -1，循环2000次后电容保持率为82.8%。该研究为高能量密度、长寿命高性能ldh的合理结构设计提供了新的思路。
{"title":"Enhanced Electrochemical Performance of NiCo-LDH by Inner Sulfur Doping Design","authors":"Junli Xu, Yujiao Li, Zhaoshun Liu, Zhongning Shi, Hongbin Sun","doi":"10.1039/d5dt02419f","DOIUrl":"https://doi.org/10.1039/d5dt02419f","url":null,"abstract":"Sulfur doping is an effective strategy to improve the rate capability and capacitance of nickelcobalt layered double hydroxide (NiCo-LDH). However, it causes a decrease in cycling stability due to the leaching of S, which further results in the dissolution of metal sites and damage of structure. In this study, only internal sulfur doped NiCo-LDH was constructed via a two-step electrodeposition method. The results show that the S doped core can enhance the materials electronic conductivity, while the pristine NiCo-LDH shell can restrict the migration of sulfur atoms from internal to interfacial, lowering sulfur and metal element dissolution losses.Moreover, the only internal S-doped NiCo-LDH structure creates a favorable interface for efficient charge transfer. These merits lead to a high specific capacitance and rate capability, as well as good cycling stability of internal S-doped NiCo-LDH. The specific capacitance is as high as 1453.42 F g -1 , and the capacitance retention rate is 82.8% after 2000 cycles. This study provides new insights into the rational structure design of high-performance LDHs with both high energy density and long lifespan.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145608846","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}
CO2 is unequivocally recognized as a greenhouse gas. In this study, we carried out a theoretical investigation of CO2 capture reactions mediated by Lewis acid/base-free G13=P double bonds embedded within the Ter–G13=P–Ter framework (Ter = 2,6-Dipp2-C6H3; Dipp = diisopropylphenyl). Several theoretical approaches were employed to evaluate their reaction barriers and chemical reactivity. Our DFT results indicate that only Ter–Al=P–Ter, Ter–Ga=P–Ter, and Ter–In=P–Ter exhibit the ability to capture CO2. The EDA analysis suggests that the bonding interaction between Ter–G13=P–Ter and CO2 in the transition state is best described by a donor–acceptor (singlet–singlet) interaction rather than an electron-sharing (triplet–triplet) interaction. FMO and NOCV analyses reveal two distinct bonding characteristics: (i) a strong forward donation from the lone pair on phosphorus to the p-π* orbital of CO2 (P → CO2), and (ii) a relatively weak back-donation from the filled p-π orbital of CO2 into the vacant orbital of the G13 center (CO2 → G13). The ASM analysis further reveals that geometrical deformation energy of CO2 plays a decisive role in determining the activation barrier of the [2 + 2] cycloaddition reaction between Ter–G13=P–Ter and CO2.
{"title":"CO₂ Activation without Metals Enabled by Lewis Acid/Base-Free G13=P Double Bonds","authors":"Ming-Der Su, Zheng-Feng Zhang","doi":"10.1039/d5dt02235e","DOIUrl":"https://doi.org/10.1039/d5dt02235e","url":null,"abstract":"CO2 is unequivocally recognized as a greenhouse gas. In this study, we carried out a theoretical investigation of CO2 capture reactions mediated by Lewis acid/base-free G13=P double bonds embedded within the Ter–G13=P–Ter framework (Ter = 2,6-Dipp2-C6H3; Dipp = diisopropylphenyl). Several theoretical approaches were employed to evaluate their reaction barriers and chemical reactivity. Our DFT results indicate that only Ter–Al=P–Ter, Ter–Ga=P–Ter, and Ter–In=P–Ter exhibit the ability to capture CO2. The EDA analysis suggests that the bonding interaction between Ter–G13=P–Ter and CO2 in the transition state is best described by a donor–acceptor (singlet–singlet) interaction rather than an electron-sharing (triplet–triplet) interaction. FMO and NOCV analyses reveal two distinct bonding characteristics: (i) a strong forward donation from the lone pair on phosphorus to the p-π* orbital of CO2 (P → CO2), and (ii) a relatively weak back-donation from the filled p-π orbital of CO2 into the vacant orbital of the G13 center (CO2 → G13). The ASM analysis further reveals that geometrical deformation energy of CO2 plays a decisive role in determining the activation barrier of the [2 + 2] cycloaddition reaction between Ter–G13=P–Ter and CO2.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"99 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145608921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The visible-light-driven photoreduction of CO2 into value-added chemicals is regarded as a promising approach to alleviating the energy crisis and addressing climate change. Heterogeneous organic photocatalysts based on π-conjugated monomers, including organic polymers/organic supramolecules composed of π-conjugation units, have demonstrated significant progress in CO2 photoreduction, attributed to their remarkable light absorption, abundant reserves of constituent elements, and tunable molecular structures. This review provides a comprehensive yet focused exploration of the general structural features of organic polymers/organic supramolecules composed of π-conjugation units, offering structure-driven design strategies tailored to address the key limitations associated with each material class in the field of CO2 photoreduction. For the organic polymers, molecular engineering, interfacial modification, and morphological control collectively overcome key thermodynamic and kinetic bottlenecks in CO2 photoreduction, leading to enhanced catalytic performance. Many of these approaches are equally applicable to organic supramolecules, wherein we further highlight the design of π-conjugated units that simultaneously serve as catalytic centers and defined sites for noncovalent interactions, and assembly strategies that enable control over aggregation states to construct precisely defined supramolecular architectures. Furnished with foundational knowledge and structure–property insights, this review predicts outstanding challenges. It outlines feasible research directions for heterogeneous organic photocatalysts based on π-conjugated monomers, offering an actionable design paradigm for advancing the rational development of next-generation organic photocatalysts for efficient solar-driven CO2 conversion.
{"title":"CO2 photoreduction with heterogeneous organic photocatalysts based on π-conjugated monomers: structure–property insights and regulation strategies","authors":"Li Yang, Yuqiang Sheng, Di Liu","doi":"10.1039/d5dt02200b","DOIUrl":"https://doi.org/10.1039/d5dt02200b","url":null,"abstract":"The visible-light-driven photoreduction of CO<small><sub>2</sub></small> into value-added chemicals is regarded as a promising approach to alleviating the energy crisis and addressing climate change. Heterogeneous organic photocatalysts based on π-conjugated monomers, including organic polymers/organic supramolecules composed of π-conjugation units, have demonstrated significant progress in CO<small><sub>2</sub></small> photoreduction, attributed to their remarkable light absorption, abundant reserves of constituent elements, and tunable molecular structures. This review provides a comprehensive yet focused exploration of the general structural features of organic polymers/organic supramolecules composed of π-conjugation units, offering structure-driven design strategies tailored to address the key limitations associated with each material class in the field of CO<small><sub>2</sub></small> photoreduction. For the organic polymers, molecular engineering, interfacial modification, and morphological control collectively overcome key thermodynamic and kinetic bottlenecks in CO<small><sub>2</sub></small> photoreduction, leading to enhanced catalytic performance. Many of these approaches are equally applicable to organic supramolecules, wherein we further highlight the design of π-conjugated units that simultaneously serve as catalytic centers and defined sites for noncovalent interactions, and assembly strategies that enable control over aggregation states to construct precisely defined supramolecular architectures. Furnished with foundational knowledge and structure–property insights, this review predicts outstanding challenges. It outlines feasible research directions for heterogeneous organic photocatalysts based on π-conjugated monomers, offering an actionable design paradigm for advancing the rational development of next-generation organic photocatalysts for efficient solar-driven CO<small><sub>2</sub></small> conversion.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145608919","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：