Qiudi Yue, Junwei Wu, Honghai Liu, Anna Kaleta, Francesco Dalena, Diogenes Honorato Piva, Pierre Ruterana, Jiaqi Zhao, Zhengxing Qin, Xionghou Gao, Zifeng Yan, Svetlana Mintova
Catalytic efficiency in zeolite-based reactions critically depends on molecular diffusion kinetics within the confined channels. Nanosized ZSM-5 zeolites with a reduced b-axis thickness shorten the diffusion path and maximize the pore-opening configuration of the straight channels, enhancing mass transfer to active sites. However, achieving precise control over such nanostructures remains challenging. Herein, we report a urea-nanoseed-assisted synthesis of ZSM-5 nanoplates with low b-axis thickness in a sustainable, fluoride-free system. Comprehensive optimization of the synthesis yielded uniform crystals with a short b-axis (30–80 nm), a-axis (75–115 nm), and c-axis (130–210 nm). Mechanistic studies revealed a reversed crystal growth pathway: crystallization initiates at amorphous aggregate surfaces and propagates inward, critically directed by the organic template in the presence of urea. In methanol-to-olefin (MTO) reactions, these nanoplates outperformed commercial ZSM-5, delivering a 30% higher propylene/ethylene ratio and doubling the catalyst's lifespan. This work provides a rational strategy for synthesizing diffusion-optimized zeolites for applications where diffusion plays a critical role.
{"title":"Seeded growth of urea-promoted ZSM-5 nanoplates with short b-axis thickness for enhanced methanol-to-olefin reactions","authors":"Qiudi Yue, Junwei Wu, Honghai Liu, Anna Kaleta, Francesco Dalena, Diogenes Honorato Piva, Pierre Ruterana, Jiaqi Zhao, Zhengxing Qin, Xionghou Gao, Zifeng Yan, Svetlana Mintova","doi":"10.1039/d5qi01888a","DOIUrl":"https://doi.org/10.1039/d5qi01888a","url":null,"abstract":"Catalytic efficiency in zeolite-based reactions critically depends on molecular diffusion kinetics within the confined channels. Nanosized ZSM-5 zeolites with a reduced <em>b</em>-axis thickness shorten the diffusion path and maximize the pore-opening configuration of the straight channels, enhancing mass transfer to active sites. However, achieving precise control over such nanostructures remains challenging. Herein, we report a urea-nanoseed-assisted synthesis of ZSM-5 nanoplates with low <em>b</em>-axis thickness in a sustainable, fluoride-free system. Comprehensive optimization of the synthesis yielded uniform crystals with a short <em>b</em>-axis (30–80 nm), <em>a</em>-axis (75–115 nm), and <em>c</em>-axis (130–210 nm). Mechanistic studies revealed a reversed crystal growth pathway: crystallization initiates at amorphous aggregate surfaces and propagates inward, critically directed by the organic template in the presence of urea. In methanol-to-olefin (MTO) reactions, these nanoplates outperformed commercial ZSM-5, delivering a 30% higher propylene/ethylene ratio and doubling the catalyst's lifespan. This work provides a rational strategy for synthesizing diffusion-optimized zeolites for applications where diffusion plays a critical role.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089617","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Actinobacteria-derived o-aminophenol oxidases (AOs) represent a largely unexplored subclass of type-III copper enzymes with catalytic properties distinct from tyrosinases and catechol oxidases. The determination of the first crystal structure of an AO (SmNspF) displays unique loop insertions and important second-sphere amino acids in vicinity of the binuclear copper center. The substrate-guiding effect of the second activity controller (HisB2+1) influences the binding affinity for carboxylcontaining substrates in the AOs SmNspF and SgGriF. Thus, kinetic investigations reveal both overlapping and distinct substrate preferences for SmNspF and SgGriF: while both enzymes oxidize monophenols, o-aminophenols, and o-diphenols, they do so at significantly different reaction rates. SmNspF preferentially oxidizes carboxylated substrates such as 3,4dihydroxybenzoic acid and 3-amino-4-hydroxybenzoic acid, whereas SgGriF exhibits higher activity toward para-methylated analogs, including 4-methylcatechol and 2-amino-4-methylphenol. Remarkably, both enzymes display enzymatic activities beyond the known AO reactivity spectrum by oxidizing 2-aminoresorcinol and o-phenylenediamine, which underlies the high versatility of the binuclear copper center. Together, these findings provide a structural basis for AO's enzymatic activity and broaden the known catalytic spectrum, which enables the prediction of catalytic properties in type-III copper proteins based on their amino acid sequence.
{"title":"Structural Insights into ortho-Aminophenol Oxidase: Kinetic and Crystallographic Characterization of SmNspF and SgGriF","authors":"Hoa Le Xuan, Annette Rompel","doi":"10.1039/d5qi02495a","DOIUrl":"https://doi.org/10.1039/d5qi02495a","url":null,"abstract":"Actinobacteria-derived o-aminophenol oxidases (AOs) represent a largely unexplored subclass of type-III copper enzymes with catalytic properties distinct from tyrosinases and catechol oxidases. The determination of the first crystal structure of an AO (SmNspF) displays unique loop insertions and important second-sphere amino acids in vicinity of the binuclear copper center. The substrate-guiding effect of the second activity controller (HisB2+1) influences the binding affinity for carboxylcontaining substrates in the AOs SmNspF and SgGriF. Thus, kinetic investigations reveal both overlapping and distinct substrate preferences for SmNspF and SgGriF: while both enzymes oxidize monophenols, o-aminophenols, and o-diphenols, they do so at significantly different reaction rates. SmNspF preferentially oxidizes carboxylated substrates such as 3,4dihydroxybenzoic acid and 3-amino-4-hydroxybenzoic acid, whereas SgGriF exhibits higher activity toward para-methylated analogs, including 4-methylcatechol and 2-amino-4-methylphenol. Remarkably, both enzymes display enzymatic activities beyond the known AO reactivity spectrum by oxidizing 2-aminoresorcinol and o-phenylenediamine, which underlies the high versatility of the binuclear copper center. Together, these findings provide a structural basis for AO's enzymatic activity and broaden the known catalytic spectrum, which enables the prediction of catalytic properties in type-III copper proteins based on their amino acid sequence.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"113 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089592","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we report a facile one-pot synthesis of a remarkably stable dication diradical of a triply fused dizinc(II)chlorin-porphyrin heterodimer along with its neutral form and free base heterodimer under a mild condition. The transformation occurs via a radical-induced oxidative rearrangement in which a dipyrromethene-bridge gets completely fused between two porphyrin macrocycles with the formation of two new C–C and one C–N bonds leading to the formation of two six membered and one seven membered rings. Two macrocycles exhibit extensive π-conjugation through the bridge which results in an antiferromagnetic coupling between the two π-cation radicals of the macrocycles. Reduction of the dication diradical complex using NaBH4 produces the neutral product which, upon demetallation under mild acidic condition (5% HCl), enable us to isolate stable, green free-base heterodimer in a quantitative yield. Due to structural rigidity and extended π-conjugation, the neutral triply-fused dimers of zinc and the freebase macrocycle display unique spectral features that includes near-IR absorption bands, narrow HOMO-LUMO band gap and intense fluorescence with increased quantum yields (ɸf). Apart from this, these dimers have displayed strong nonlinear optical properties involving two photon absorption due to their rigid π-conjugated structures while the Zn complex display much higher TPA (σ2) values than their Ni and Cu analogs. In contrast to the neutral heterodimer, large enhancement in the TPA coefficient was observed for their singlet dication diradical complex with the same structural framework.
{"title":"Facile One-pot Synthesis of Triply-Fused, Fluorescent Chlorin-porphyrin Heterodimers with Near-IR Absorption: Impact of π-Conjugation on Optical Properties","authors":"Syed Jehanger Shah, Aman Sharma, Basanta Khamrui, Arya Roychowdhury, Debabrata Goswami, Sankar Prasad Rath","doi":"10.1039/d5qi02369f","DOIUrl":"https://doi.org/10.1039/d5qi02369f","url":null,"abstract":"Herein, we report a facile one-pot synthesis of a remarkably stable dication diradical of a triply fused dizinc(II)chlorin-porphyrin heterodimer along with its neutral form and free base heterodimer under a mild condition. The transformation occurs via a radical-induced oxidative rearrangement in which a dipyrromethene-bridge gets completely fused between two porphyrin macrocycles with the formation of two new C–C and one C–N bonds leading to the formation of two six membered and one seven membered rings. Two macrocycles exhibit extensive π-conjugation through the bridge which results in an antiferromagnetic coupling between the two π-cation radicals of the macrocycles. Reduction of the dication diradical complex using NaBH4 produces the neutral product which, upon demetallation under mild acidic condition (5% HCl), enable us to isolate stable, green free-base heterodimer in a quantitative yield. Due to structural rigidity and extended π-conjugation, the neutral triply-fused dimers of zinc and the freebase macrocycle display unique spectral features that includes near-IR absorption bands, narrow HOMO-LUMO band gap and intense fluorescence with increased quantum yields (ɸf). Apart from this, these dimers have displayed strong nonlinear optical properties involving two photon absorption due to their rigid π-conjugated structures while the Zn complex display much higher TPA (σ2) values than their Ni and Cu analogs. In contrast to the neutral heterodimer, large enhancement in the TPA coefficient was observed for their singlet dication diradical complex with the same structural framework.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"117 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070564","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Bo Zhang, Qiqi Zhang, Ru Xiao, Xiaoxuan Min, Huiqi Jia, Kang Liu, Ying Deng, Zhenyu Xiao, Lei Wang
The development of high-performance chlorine evolution reaction (CER) catalysts with low noble metal content, superior selectivity, and excellent stability is urgently needed to address the limitations of commercial Ru/Ir-based catalysts, such as high cost, severe OER competition, and nanoparticle instability. In this study, an innovative strategy is employed to fabricate a CoRu@CN catalyst by leveraging polydopamine-derived nitrogen-doped carbon nanospheres to immobilize cobalt–ruthenium (CoRu) alloy nanoparticles through robust metal–nitrogen coordination bonds, while optimizing the electronic structure via bimetallic synergy and nitrogen-induced modulation. The as-prepared CoRu@CN catalyst exhibits outstanding CER performance, with a remarkably low overpotential of 154 mV at 100 mA cm−2, a favorable Tafel slope of 68.18 mV dec−1, and a high chlorine selectivity of 97–99% in 5 M NaCl (pH = 2), along with a 3.8-fold enhancement in the electrochemically active surface area, attributed to the defect-rich active sites generated by doping. Mechanistic investigations reveal that CoRu@CN operates via the Volmer–Krishtalik (V–K) pathway, where the kinetics of the rate-determining Krishtalik step is significantly promoted at elevated potentials. Meanwhile, the nitrogen-doped carbon scaffold not only suppresses nanoparticle agglomeration and phase separation through metal–nitrogen coordination but also enhances mass transport and conductivity, contributing to the catalyst's exceptional durability with 99.3% activity retention after 100 hours of testing. This work not only solves the long-standing industrial problem of nanoparticle instability in CER catalysis but also provides a novel design strategy for developing corrosion-resistant, high-efficiency electrocatalysts, highlighting the potential of CoRu@CN for scalable and energy-efficient chlor-alkali electrolysis.
开发具有低贵金属含量、高选择性和优异稳定性的高性能氯释放反应（CER）催化剂是迫切需要的，以解决商用Ru/ ir催化剂成本高、OER竞争激烈和纳米颗粒不稳定性等局限性。本研究采用创新策略，利用聚多巴胺衍生的氮掺杂碳纳米球通过稳健的金属-氮配位键固定钴钌（CoRu）合金纳米颗粒，同时通过双金属协同作用和氮诱导调制优化电子结构，制备CoRu@CN催化剂。制备的CoRu@CN催化剂表现出优异的CER性能，在100 mA cm−2下过电位为154 mV， Tafel斜率为68.18 mV dec−1，在5 M NaCl （pH = 2）中氯选择性为97-99%，并且由于掺杂产生了富含缺陷的活性位点，电化学活性表面积提高了3.8倍。机制研究表明CoRu@CN通过volmer - krisshtalik （V-K）途径起作用，在该途径中，决定速率的krisshtalik步骤的动力学在电位升高时显着促进。同时，氮掺杂碳支架不仅通过金属-氮配位抑制纳米颗粒团聚和相分离，还增强了质量传递和导电性，有助于催化剂在100小时测试后保持99.3%的活性保持。这项工作不仅解决了CER催化中纳米颗粒不稳定的长期工业问题，而且为开发耐腐蚀、高效的电催化剂提供了一种新的设计策略，突出了CoRu@CN在可扩展和节能的氯碱电解中的潜力。
{"title":"A strain-modulated CoRu alloy supported on nitrogen-doped carbon nanospheres for defect-driven industrial chlorine evolution electrocatalysis","authors":"Bo Zhang, Qiqi Zhang, Ru Xiao, Xiaoxuan Min, Huiqi Jia, Kang Liu, Ying Deng, Zhenyu Xiao, Lei Wang","doi":"10.1039/d5qi02151k","DOIUrl":"https://doi.org/10.1039/d5qi02151k","url":null,"abstract":"The development of high-performance chlorine evolution reaction (CER) catalysts with low noble metal content, superior selectivity, and excellent stability is urgently needed to address the limitations of commercial Ru/Ir-based catalysts, such as high cost, severe OER competition, and nanoparticle instability. In this study, an innovative strategy is employed to fabricate a CoRu@CN catalyst by leveraging polydopamine-derived nitrogen-doped carbon nanospheres to immobilize cobalt–ruthenium (CoRu) alloy nanoparticles through robust metal–nitrogen coordination bonds, while optimizing the electronic structure <em>via</em> bimetallic synergy and nitrogen-induced modulation. The as-prepared CoRu@CN catalyst exhibits outstanding CER performance, with a remarkably low overpotential of 154 mV at 100 mA cm<small><sup>−2</sup></small>, a favorable Tafel slope of 68.18 mV dec<small><sup>−1</sup></small>, and a high chlorine selectivity of 97–99% in 5 M NaCl (pH = 2), along with a 3.8-fold enhancement in the electrochemically active surface area, attributed to the defect-rich active sites generated by doping. Mechanistic investigations reveal that CoRu@CN operates <em>via</em> the Volmer–Krishtalik (V–K) pathway, where the kinetics of the rate-determining Krishtalik step is significantly promoted at elevated potentials. Meanwhile, the nitrogen-doped carbon scaffold not only suppresses nanoparticle agglomeration and phase separation through metal–nitrogen coordination but also enhances mass transport and conductivity, contributing to the catalyst's exceptional durability with 99.3% activity retention after 100 hours of testing. This work not only solves the long-standing industrial problem of nanoparticle instability in CER catalysis but also provides a novel design strategy for developing corrosion-resistant, high-efficiency electrocatalysts, highlighting the potential of CoRu@CN for scalable and energy-efficient chlor-alkali electrolysis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089593","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Driven by the global carbon neutrality strategy, the efficient catalytic conversion of CO2 is a crucial component for achieving the recycling of carbon resources. However, conventional catalysts are limited by issues such as single active sites, insufficient stability, and low energy efficiency, making it difficult to meet the demands of industrial-scale applications. High-entropy materials (HEMs), a novel class of functional systems composed of five or more principal elements, offer a promising breakthrough for CO2 reduction reaction (CO2 RR) catalysts. They leverage the structural stability conferred by the high-entropy effect, synergistic regulation from multi-component systems, and tunable electronic structures. This article systematically reviews the recent advancements in high-entropy alloys (HEAs), high-entropy oxides (HEOs), high-entropy sulfides (HESs), and other HEMs for CO2 RR via photocatalytic, electrocatalytic, and thermocatalytic pathways. It further explores the application of machine learning-driven high-throughput design strategies and component modulation methods in HEMs development. Focusing on the promising HEMs, this review establishes a theoretical framework for designing next-generation CO2 RR catalysts, providing critical guidance for carbon neutrality advancements.
{"title":"Emerging Frontiers of High-Entropy Materials for Catalytic CO2 Reduction","authors":"Jiale Wang, Lingzhi Yang, Yuan Chen, Wanting Zhang, Pengyan Li, Hongda Li","doi":"10.1039/d6qi00011h","DOIUrl":"https://doi.org/10.1039/d6qi00011h","url":null,"abstract":"Driven by the global carbon neutrality strategy, the efficient catalytic conversion of CO2 is a crucial component for achieving the recycling of carbon resources. However, conventional catalysts are limited by issues such as single active sites, insufficient stability, and low energy efficiency, making it difficult to meet the demands of industrial-scale applications. High-entropy materials (HEMs), a novel class of functional systems composed of five or more principal elements, offer a promising breakthrough for CO2 reduction reaction (CO2 RR) catalysts. They leverage the structural stability conferred by the high-entropy effect, synergistic regulation from multi-component systems, and tunable electronic structures. This article systematically reviews the recent advancements in high-entropy alloys (HEAs), high-entropy oxides (HEOs), high-entropy sulfides (HESs), and other HEMs for CO2 RR via photocatalytic, electrocatalytic, and thermocatalytic pathways. It further explores the application of machine learning-driven high-throughput design strategies and component modulation methods in HEMs development. Focusing on the promising HEMs, this review establishes a theoretical framework for designing next-generation CO2 RR catalysts, providing critical guidance for carbon neutrality advancements.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"79 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jaison CASAS, Shaban RAJA MUHAMMAD, David PIANCA, Nolwenn Le Breton, Sylvie Choua, Nathalie Kyritsakas, Christophe Gourlaouen, Abdelaziz Jouaiti, Sylvie Ferlay
The formation of two parent divergent ligands derived from 1,4-bis(pyrid-3-yl)benzene is reported. The synthetic route involves condensation of alloxan with a dibromodiamine precursor, followed by benzylation, leading, after Suzuki-Miyaura cross-coupling reaction, to the formation of two ligands: L1, bearing the well-known pteridine-dione moiety, and L2, in which ring contraction and symmetrisation occur, resulting in an imidazopyrazinone core. The synthesis of L1 and L2, along with their characterization in solution and in the solid state, is reported. Electrochemical studies of L1 and L2 solutions revealed analogous two-electron reduction processes, with the first reduction step leading to radical species, as confirmed by EPR spectroelectrochemistry. For L1, the first and second reductions occur at at ERed1= −0,80 V and ERed2= −1.35 V vs Ag/AgCl, in agreement with values reported for other pteridine-dione species, whereas L2 displays more negative reduction potentials, shifted by approximately 0.7 V. These observations were confirmed by DFT calculations. The coordination abilities of L1 and L2 were investigated. Single-crystal X-ray diffraction (XSCXRD) revealed the formation of a pillared 3D compound, L2-Zn, obtained by mixing L2, 4,4'-Biphenyldicarboxylic acid (H2bpdc) and a Zn2+ salt in solvothermal conditions. A series of powdered isostructural L2-M compounds (M = Zn, Ni, Co) was synthesized and characterized by Powder X-ray diffractio (PXRD). Under the same conditions, using L1 instead of L2 led to the formation of poorly diffracting crystals, which nevertheless exhibited a three-dimensional pillared architecture. A complete series of powdered isostructural L1-M compounds (M= Co, Ni, Cu and Zn) was evidenced. The solid-state electrochemical behavior of the L2-M analogues (M = Zn and Co) was investigated, revealing ligand-based reduction processes occuring within the three-dimensional pillared structure for both L2-Zn and L2-Co.
{"title":"Cycle contraction and symmetrisation in Redox-active ligands: from alloxazine to isoimidazolonequinoxaline derivatives, and their electrochemical and coordination studies","authors":"Jaison CASAS, Shaban RAJA MUHAMMAD, David PIANCA, Nolwenn Le Breton, Sylvie Choua, Nathalie Kyritsakas, Christophe Gourlaouen, Abdelaziz Jouaiti, Sylvie Ferlay","doi":"10.1039/d5qi02572a","DOIUrl":"https://doi.org/10.1039/d5qi02572a","url":null,"abstract":"The formation of two parent divergent ligands derived from 1,4-bis(pyrid-3-yl)benzene is reported. The synthetic route involves condensation of alloxan with a dibromodiamine precursor, followed by benzylation, leading, after Suzuki-Miyaura cross-coupling reaction, to the formation of two ligands: L1, bearing the well-known pteridine-dione moiety, and L2, in which ring contraction and symmetrisation occur, resulting in an imidazopyrazinone core. The synthesis of L1 and L2, along with their characterization in solution and in the solid state, is reported. Electrochemical studies of L1 and L2 solutions revealed analogous two-electron reduction processes, with the first reduction step leading to radical species, as confirmed by EPR spectroelectrochemistry. For L1, the first and second reductions occur at at ERed1= −0,80 V and ERed2= −1.35 V vs Ag/AgCl, in agreement with values reported for other pteridine-dione species, whereas L2 displays more negative reduction potentials, shifted by approximately 0.7 V. These observations were confirmed by DFT calculations. The coordination abilities of L1 and L2 were investigated. Single-crystal X-ray diffraction (XSCXRD) revealed the formation of a pillared 3D compound, L2-Zn, obtained by mixing L2, 4,4'-Biphenyldicarboxylic acid (H2bpdc) and a Zn2+ salt in solvothermal conditions. A series of powdered isostructural L2-M compounds (M = Zn, Ni, Co) was synthesized and characterized by Powder X-ray diffractio (PXRD). Under the same conditions, using L1 instead of L2 led to the formation of poorly diffracting crystals, which nevertheless exhibited a three-dimensional pillared architecture. A complete series of powdered isostructural L1-M compounds (M= Co, Ni, Cu and Zn) was evidenced. The solid-state electrochemical behavior of the L2-M analogues (M = Zn and Co) was investigated, revealing ligand-based reduction processes occuring within the three-dimensional pillared structure for both L2-Zn and L2-Co.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057084","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Young Hoon Lee, Rafi Muhammad Lutfi, Junseong Lee, Eunsung Lee, Jaehoon Jung, Min Hyung Lee
Precise control over the emissive excited states of luminophores is crucial for advancing high-performance optoelectronic materials. Herein, we present a facile strategy for tuning the emissive excited states of o-carborane-functionalized B,N-doped multi-resonance thermally activated delayed fluorescence (MR-TADF) compounds through steric modulation of 2-R substituents. A series of 2-R-o-carboranyl MR-TADF compounds, denoted DtBuCzB-CBR, were synthesized and characterized with substituents of varying steric demand at the 2-position of the o-carborane cage (R = H (1), Me (2), iBu (3), and SiMe3 (TMS, 4)). Single-crystal X-ray analyses of compounds 2 and 4 revealed a nearly perpendicular orientation of the o-carboranyl C-C bond relative to the MR core plane, with compound 4 showing greater C-C bond elongation and structural distortion than 2. Notably, the compounds exhibit either single (1) or dual emission (2-4) in both solution and rigid states, depending on the steric bulk of the 2-R substituent. Theoretical calculations suggest that the single emission originates from a locally excited short-range charge transfer (SRCT) state confined within the MR core, whereas dual emission arises from both the SRCT state and a lower-energy hybridized local and charge transfer (HLCT) state, facilitated by electronic coupling between the MR core and the o-carborane unit. The emergence and persistence of the emissive HLCT state correlate with increased steric hindrance at the 2-position, which induces elongation of the o-carboranyl C-C bond and restricts cage rotation in the excited state. These findings provide a new design principle for o-carborane-based luminophores with tunable excited-state emission characteristics.
精确控制发光团的发射激发态对于推进高性能光电材料至关重要。在此，我们提出了一种简单的策略，通过2-R取代基的立体调制来调节邻碳硼烷功能化B， n掺杂的多共振热激活延迟荧光（MR-TADF）化合物的发射激发态。合成了一系列2-R-o-碳硼基MR-TADF化合物，命名为DtBuCzB-CBR，并在o-碳硼烷笼的2位上用不同空间需求的取代基(R = H (1), Me (2), iBu（3)和SiMe3 (TMS, 4)）进行了表征。化合物2和4的单晶x射线分析显示，o-碳烷基C-C键的取向与MR核心面几乎垂直，化合物4的C-C键伸长率和结构畸变比2大。值得注意的是，根据2-R取代基的空间体积，化合物在溶液态和刚性态均表现出单(1)或双（2-4）发射。理论计算表明，单发射源于局限在磁核内的局部激发短程电荷转移（SRCT）状态，而双发射源于SRCT状态和低能量杂化局部和电荷转移（HLCT）状态，这是由磁核和o-碳硼烷单元之间的电子耦合促进的。发射型HLCT态的出现和持续与2位空间位阻的增加有关，这导致了o-碳烷基C-C键的伸长，并限制了激发态的笼形旋转。这些发现为具有可调激发态发射特性的邻碳硼烷基发光团提供了新的设计原理。
{"title":"Steric modulation of o-carborane enables tunable single and dual emission in multi-resonance TADF compounds","authors":"Young Hoon Lee, Rafi Muhammad Lutfi, Junseong Lee, Eunsung Lee, Jaehoon Jung, Min Hyung Lee","doi":"10.1039/d5qi02417j","DOIUrl":"https://doi.org/10.1039/d5qi02417j","url":null,"abstract":"Precise control over the emissive excited states of luminophores is crucial for advancing high-performance optoelectronic materials. Herein, we present a facile strategy for tuning the emissive excited states of <em>o</em>-carborane-functionalized B,N-doped multi-resonance thermally activated delayed fluorescence (MR-TADF) compounds through steric modulation of 2-R substituents. A series of 2-R-<em>o</em>-carboranyl MR-TADF compounds, denoted DtBuCzB-CBR, were synthesized and characterized with substituents of varying steric demand at the 2-position of the o-carborane cage (R = H (<strong>1</strong>), Me (<strong>2</strong>), <small><sup><em>i</em></sup></small>Bu (<strong>3</strong>), and SiMe<small><sub>3</sub></small> (TMS, <strong>4</strong>)). Single-crystal X-ray analyses of compounds <strong>2 </strong>and <strong>4 </strong>revealed a nearly perpendicular orientation of the <em>o</em>-carboranyl C-C bond relative to the MR core plane, with compound <strong>4 </strong>showing greater C-C bond elongation and structural distortion than <strong>2</strong>. Notably, the compounds exhibit either single (<strong>1</strong>) or dual emission (<strong>2</strong>-<strong>4</strong>) in both solution and rigid states, depending on the steric bulk of the 2-R substituent. Theoretical calculations suggest that the single emission originates from a locally excited short-range charge transfer (SRCT) state confined within the MR core, whereas dual emission arises from both the SRCT state and a lower-energy hybridized local and charge transfer (HLCT) state, facilitated by electronic coupling between the MR core and the <em>o</em>-carborane unit. The emergence and persistence of the emissive HLCT state correlate with increased steric hindrance at the 2-position, which induces elongation of the <em>o</em>-carboranyl C-C bond and restricts cage rotation in the excited state. These findings provide a new design principle for <em>o</em>-carborane-based luminophores with tunable excited-state emission characteristics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"17 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070565","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luana Daniel, Chris Hebert Jesus Franco, Adrielle Sacramento de Morais, Arquimedes Karam, Marcelo Cecconi Portes, Milena Barros Silva, Cristiane Barata-Silva, Lisia Maria Gobbo, Joel Mosnier, Isabelle Fonta, Ana Maria Da Costa Ferreira, Bruno Pradines, Diogo R Moreira, Maribel Navarro
Five novel metal-based complexes of Ag(I) [Ag(ATV)] (1), Zn(II) [Zn(ATV)2(H2O)2]·2H2O (2), [Zn(ATV)2(CH3OH)2]·H2O (3), {Zn(ATV)2}ₙ (4), and Cu(II) [Cu(ATV)₂] (5), with the antimalarial naphthoquinone atovaquone (ATV) as a ligand were synthesized and characterized. Ag(I) and Cu(II) complexes were thoroughly analyzed using IR, NMR, EPR, and conductivity measurements, whereas the crystal structures of the three Zn(II) complexes were determined by single-crystal X-ray diffraction, supported by complementary analytical techniques. Depending on the metal center, ATV coordinates in either a monodentate or bidentate coordination mode, producing highly stable metal complexes both in the solid state and in DMSO solution. These metal-ATV complexes retain the potent antiplasmodial activity of ATV against chloroquine-sensitive and-resistant Plasmodium falciparum strains while introducing additional mechanisms of action. Zn(II) complexes inhibit β-hematin formation based on FTIR, complex 3, accelerates ring-stage parasite killing, and complex 5, promotes intracellular copper accumulation, correlating with enhanced antiplasmodial potency. These results demonstrate that metal coordination can finely tune the biological profile of ATV, positioning these compounds as promising leads for the design of new antimalarial drugs.
{"title":"Metal-atovaquone complexes with antiplasmodial activity: chemical reactivity and structure-activity relationships","authors":"Luana Daniel, Chris Hebert Jesus Franco, Adrielle Sacramento de Morais, Arquimedes Karam, Marcelo Cecconi Portes, Milena Barros Silva, Cristiane Barata-Silva, Lisia Maria Gobbo, Joel Mosnier, Isabelle Fonta, Ana Maria Da Costa Ferreira, Bruno Pradines, Diogo R Moreira, Maribel Navarro","doi":"10.1039/d5qi02161h","DOIUrl":"https://doi.org/10.1039/d5qi02161h","url":null,"abstract":"Five novel metal-based complexes of Ag(I) [Ag(ATV)] (1), Zn(II) [Zn(ATV)2(H2O)2]·2H2O (2), [Zn(ATV)2(CH3OH)2]·H2O (3), {Zn(ATV)2}ₙ (4), and Cu(II) [Cu(ATV)₂] (5), with the antimalarial naphthoquinone atovaquone (ATV) as a ligand were synthesized and characterized. Ag(I) and Cu(II) complexes were thoroughly analyzed using IR, NMR, EPR, and conductivity measurements, whereas the crystal structures of the three Zn(II) complexes were determined by single-crystal X-ray diffraction, supported by complementary analytical techniques. Depending on the metal center, ATV coordinates in either a monodentate or bidentate coordination mode, producing highly stable metal complexes both in the solid state and in DMSO solution. These metal-ATV complexes retain the potent antiplasmodial activity of ATV against chloroquine-sensitive and-resistant Plasmodium falciparum strains while introducing additional mechanisms of action. Zn(II) complexes inhibit β-hematin formation based on FTIR, complex 3, accelerates ring-stage parasite killing, and complex 5, promotes intracellular copper accumulation, correlating with enhanced antiplasmodial potency. These results demonstrate that metal coordination can finely tune the biological profile of ATV, positioning these compounds as promising leads for the design of new antimalarial drugs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"49 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The rapid global shift toward low-carbon technologies necessitates the development of cost-effective and sustainable catalytic systems to support the emerging methanol economy. At the same time, large volumes of spent refinery catalysts (aka Fluid Catalytic Cracking (FCC) catalysts) are routinely discarded, posing both environmental and economic challenges. We benchmark fresh and equilibrium FCC catalysts in methanol-to-hydrocarbons (MTH) reactions and demonstrate that industrial aging alters textural properties, acid-site distribution, and methanol-activation pathways. Integrated advanced characterization, including operando measurements and solid-state NMR studies, links regeneration-induced structural degradation to altered catalytic behavior and mechanism. Both catalysts show high initial methanol conversion, but the spent FCC catalyst (Ecat) deactivates quickly and produces more methane due to leftover metals and lower acidity. The fresh FCC catalyst is more stable, makes relatively more light olefins and paraffins, and forms less coke. Mechanistic studies show the fresh catalyst forms more useful reaction intermediates, while Ecat traps heavier, less reactive species, leading to faster deactivation. This study shows how industrial aging reshapes catalytic routes and deactivation, enabling the reuse or retuning of spent (equilibrium) catalysts for low-carbon MTH and guiding the design of efficient, waste-derived catalysts for a circular C1 economy.
{"title":"Repurposing Fluid Catalytic Cracking Catalysts for Methanol Conversion: Route Selection and Deactivation Fingerprints","authors":"Yunfan Wang, Xin Zhang, Jiaqi Zhao, Xinyu You, Jiangcheng Li, Zhengxing Qin, Abhishek Dutta Chowdhury","doi":"10.1039/d5qi02418h","DOIUrl":"https://doi.org/10.1039/d5qi02418h","url":null,"abstract":"The rapid global shift toward low-carbon technologies necessitates the development of cost-effective and sustainable catalytic systems to support the emerging methanol economy. At the same time, large volumes of spent refinery catalysts (aka Fluid Catalytic Cracking (FCC) catalysts) are routinely discarded, posing both environmental and economic challenges. We benchmark fresh and equilibrium FCC catalysts in methanol-to-hydrocarbons (MTH) reactions and demonstrate that industrial aging alters textural properties, acid-site distribution, and methanol-activation pathways. Integrated advanced characterization, including operando measurements and solid-state NMR studies, links regeneration-induced structural degradation to altered catalytic behavior and mechanism. Both catalysts show high initial methanol conversion, but the spent FCC catalyst (Ecat) deactivates quickly and produces more methane due to leftover metals and lower acidity. The fresh FCC catalyst is more stable, makes relatively more light olefins and paraffins, and forms less coke. Mechanistic studies show the fresh catalyst forms more useful reaction intermediates, while Ecat traps heavier, less reactive species, leading to faster deactivation. This study shows how industrial aging reshapes catalytic routes and deactivation, enabling the reuse or retuning of spent (equilibrium) catalysts for low-carbon MTH and guiding the design of efficient, waste-derived catalysts for a circular C1 economy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"30 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The construction of a novel, low-cost, anoxic catalytic oxidation system, in which light-assisted heterogeneous catalysis is employed to regulate the activation of H2O2, holds potential application value for water purification. In this study, an oxygen-free FeWO4@CN/H2O2/Vis system was designed for the advanced treatment of ofloxacin (OFL)-contaminated wastewater. XPS, ESR, and UPS analyses demonstrated that the S-scheme charge transfer pathway greatly accelerated the charge transfer rate within the heterojunction. The FeWO4@CN-20 photocatalyst demonstrated 99% removal of OFL within 20 minutes, significantly outperforming monomeric CN. The degradation rate of OFL by FeWO4@CN-20 was approximately 7.5 times higher than that by CN and 10.8 times higher than that by FeWO4. ROS -capturing experiments in an anaerobic environment revealed that the generated ˙O2− and 1O2 played predominant roles in degrading OFL. Moreover, the Fe2+/Fe3+ redox cycle synergistically enhanced H2O2 activation, ensuring both the efficiency and stability of the photo-Fenton reaction. In situ Raman and ESR spectroscopies further revealed the catalytic mechanism by which synergistic visible-light irradiation enhanced the H2O2 activation efficiency. Continuous membrane reactor experiments confirmed that the FeWO4@CN/H2O2/Vis system significantly enhanced photo-Fenton activity and OFL degradation stability compared with the FeWO4@CN/H2O2 and CN/H2O2/Vis systems. Moreover, the FeWO4@CN/H2O2/Vis system not only exhibited photothermal effects but also showed excellent resistance to ion interference and continuous degradation under hypoxic conditions. The degradation products exhibited low or no toxicity, suggesting the system's potential for practical applications. Overall, this study offers valuable insights into the development of heterojunction photocatalysts to remediate fluoroquinolone antibiotic pollutants in aquatic environments.
{"title":"Oxygen-free wastewater treatment system constructed using FeWO4@CN S-scheme heterojunction photocatalyst coupled with H2O2 activation","authors":"Weipeng Liu, Fengmei Yang, Yuanguo Xu, Puyang Zhou, Yan Wang, Changkun Xia, Yilin Deng, Guisheng Zhu, Meng Xie","doi":"10.1039/d5qi02125a","DOIUrl":"https://doi.org/10.1039/d5qi02125a","url":null,"abstract":"The construction of a novel, low-cost, anoxic catalytic oxidation system, in which light-assisted heterogeneous catalysis is employed to regulate the activation of H<small><sub>2</sub></small>O<small><sub>2</sub></small>, holds potential application value for water purification. In this study, an oxygen-free FeWO<small><sub>4</sub></small>@CN/H<small><sub>2</sub></small>O<small><sub>2</sub></small>/Vis system was designed for the advanced treatment of ofloxacin (OFL)-contaminated wastewater. XPS, ESR, and UPS analyses demonstrated that the S-scheme charge transfer pathway greatly accelerated the charge transfer rate within the heterojunction. The FeWO<small><sub>4</sub></small>@CN-20 photocatalyst demonstrated 99% removal of OFL within 20 minutes, significantly outperforming monomeric CN. The degradation rate of OFL by FeWO<small><sub>4</sub></small>@CN-20 was approximately 7.5 times higher than that by CN and 10.8 times higher than that by FeWO<small><sub>4</sub></small>. ROS -capturing experiments in an anaerobic environment revealed that the generated ˙O<small><sub>2</sub></small><small><sup>−</sup></small> and <small><sup>1</sup></small>O<small><sub>2</sub></small> played predominant roles in degrading OFL. Moreover, the Fe<small><sup>2+</sup></small>/Fe<small><sup>3+</sup></small> redox cycle synergistically enhanced H<small><sub>2</sub></small>O<small><sub>2</sub></small> activation, ensuring both the efficiency and stability of the photo-Fenton reaction. In situ Raman and ESR spectroscopies further revealed the catalytic mechanism by which synergistic visible-light irradiation enhanced the H<small><sub>2</sub></small>O<small><sub>2</sub></small> activation efficiency. Continuous membrane reactor experiments confirmed that the FeWO<small><sub>4</sub></small>@CN/H<small><sub>2</sub></small>O<small><sub>2</sub></small>/Vis system significantly enhanced photo-Fenton activity and OFL degradation stability compared with the FeWO<small><sub>4</sub></small>@CN/H<small><sub>2</sub></small>O<small><sub>2</sub></small> and CN/H<small><sub>2</sub></small>O<small><sub>2</sub></small>/Vis systems. Moreover, the FeWO<small><sub>4</sub></small>@CN/H<small><sub>2</sub></small>O<small><sub>2</sub></small>/Vis system not only exhibited photothermal effects but also showed excellent resistance to ion interference and continuous degradation under hypoxic conditions. The degradation products exhibited low or no toxicity, suggesting the system's potential for practical applications. Overall, this study offers valuable insights into the development of heterojunction photocatalysts to remediate fluoroquinolone antibiotic pollutants in aquatic environments.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"101 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034158","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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