Mike S. B. Jørgensen, Kasper Enemark-Rasmussen, Mariusz Kubus, René W. Larsen, Martin Nielsen
We report the synthesis and analysis of five-coordinate 18-electron (formally) PNP–Ru(0) halido nitrosyl complexes (PNP)RuX(NO) (X = I, Br, Cl). These compounds show substantial geometric deviation from literature-reported isoelectronic analogs. Instead of the typical trigonal bipyramidal or square pyramidal structures, they adopt a Y-shaped distorted trigonal bipyramidal geometry, which is unprecedented for formal d8 complexes. Demonstrating further non-classical behavior, in the distorted trigonal plane, the π-donating halido ligand (X) and the PNP amine form the acute bond angle, while the π-accepting NO resides in the obtuse coordination site, and it is evident from SC-XRD, IR, and multinuclear NMR spectroscopy that the nature of the X ligand influences the degree of distortion. In addition to the spectroscopic and crystallographic analyses, the nature of the rare and, for 5-coordinate species, unprecedented X–Ru(0) bond is assessed by means of natural population analysis and orbital interactions. The computational and spectroscopic results show a clear dependence on the π-donating capability and the electronegativity of the X ligand. Finally, DFT analysis of the hypothetical structures (PNP)RuF(NO) and (PNP)Ru(OMe)(NO) at the PBE0 and TPSSh levels of theory corroborated our experimental findings.
本文报道了五坐标18电子（正式）PNP - ru(0)卤代亚硝基配合物（PNP）RuX(NO) （X = I, Br, Cl）的合成和分析。这些化合物与文献报道的等电子类似物有很大的几何偏差。它们不是典型的三角双锥体或方形锥体结构，而是采用了y形畸变三角双锥体几何结构，这在正式的d8配合物中是前所未有的。进一步证明了非经典行为，在扭曲的三角平面上，供π的halido配体(X)与PNP胺形成急性键角，而接受π的NO位于钝角配位，从SC-XRD， IR和多核核磁共振光谱中可以明显看出，X配体的性质影响了扭曲程度。除了光谱和晶体学分析外，还通过自然种群分析和轨道相互作用评估了罕见的，对于5坐标物种来说，前所未有的X-Ru(0)键的性质。计算结果和光谱结果表明，配体的给π能力和电负性明显依赖于配体。最后，在理论的PBE0和TPSSh水平上对假设结构（PNP）RuF（NO）和（PNP）Ru(OMe)（NO）的DFT分析证实了我们的实验结果。
{"title":"Novel stereoelectronic properties of 5-coordinate ruthenium(0) complexes","authors":"Mike S. B. Jørgensen, Kasper Enemark-Rasmussen, Mariusz Kubus, René W. Larsen, Martin Nielsen","doi":"10.1039/d5qi02423d","DOIUrl":"https://doi.org/10.1039/d5qi02423d","url":null,"abstract":"We report the synthesis and analysis of five-coordinate 18-electron (<em>formally</em>) PNP–Ru(0) halido nitrosyl complexes (PNP)RuX(NO) (X = I, Br, Cl). These compounds show substantial geometric deviation from literature-reported isoelectronic analogs. Instead of the typical trigonal bipyramidal or square pyramidal structures, they adopt a Y-shaped distorted trigonal bipyramidal geometry, which is unprecedented for formal <em>d</em><small><sup>8</sup></small> complexes. Demonstrating further non-classical behavior, in the distorted trigonal plane, the π-donating halido ligand (X) and the PNP amine form the acute bond angle, while the π-accepting NO resides in the obtuse coordination site, and it is evident from SC-XRD, IR, and multinuclear NMR spectroscopy that the nature of the X ligand influences the degree of distortion. In addition to the spectroscopic and crystallographic analyses, the nature of the rare and, for 5-coordinate species, unprecedented X–Ru(0) bond is assessed by means of natural population analysis and orbital interactions. The computational and spectroscopic results show a clear dependence on the π-donating capability and the electronegativity of the X ligand. Finally, DFT analysis of the hypothetical structures (PNP)RuF(NO) and (PNP)Ru(OMe)(NO) at the PBE0 and TPSSh levels of theory corroborated our experimental findings.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471107","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}
Juan Carlos Pérez-Sánchez, Jesús Moradell, Juan V. Alegre-Requena, Raquel P. Herrera, M. Concepción Gimeno
We report an unprecedented gold(III)-templated insertion of selenium and tellurium into Au–P bonds of bis(diphenylphosphane)methane (dppm), affording the first examples of κ²-(E,P) Au(III) metallacycles (E = Se, Te) via direct chalcogen transfer under mild conditions. This transformation represents a rare case of heavy-chalcogen incorporation into a metal–phosphorus bond, providing synthetic access to previously elusive Te-functional diphosphanes and extending to their selenium congeners. Structural, spectroscopic, and computational analyses reveal that Au coordination modulates P–E covalency and charge distribution, yielding electronically diverse chalcogenated frameworks. Beyond synthetic novelty, these Au–E–P scaffolds act as potent chalcogen-bond (ChB) donors in transfer hydrogenation, with Te complexes outperforming their Se analogues in line with deeper, more accessible Te σ-holes. Remarkably, their catalytic efficiency parallels that of metal-free phosphonium chalcogenides, prepared by direct methylation of (iPr)₃P=E for comparative evaluation. The synergy between Au coordination and chalcogen identity furnishes direct access to otherwise inaccessible Te-functional diphosphanes and establishes a modular platform for tuning σ-hole interactions, advancing the design of main-group/transition-metal hybrids for noncovalent catalysis and molecular materials.
我们报道了一种前所未有的金（III）模板将硒和碲插入到双（二苯基膦）甲烷（dppm）的Au - P键中，在温和条件下通过直接硫转移提供了κ²-(E，P) Au（III）金属循环（E = Se, Te）的第一个例子。这种转变代表了重硫结合到金属-磷键中的罕见情况，为以前难以捉摸的te功能二磷化提供了合成途径，并扩展到它们的硒同源物。结构、光谱和计算分析表明，Au配位调节P-E共价和电荷分布，产生电子上不同的硫代框架。除了合成新颖之外，这些Au-E-P支架在转移氢化过程中充当了强有力的硫键（ChB）供体，Te配合物的性能优于Se类似物，因为它们具有更深、更容易获得的Te σ-孔。值得注意的是，它们的催化效率与通过（iPr）₃P=E直接甲基化制备的无金属硫族膦的催化效率相似，以进行比较评价。金配位和硫同一性之间的协同作用提供了直接获取难以获得的te官能团二膦的途径，并为调整σ-空穴相互作用建立了模块化平台，推进了用于非共价催化和分子材料的主族/过渡金属杂化物的设计。
{"title":"Gold(III)-Mediated Insertion of Se and Te into Au–P Bonds: En route to Diphosphane Chalcogenides and σ-Hole Modulation","authors":"Juan Carlos Pérez-Sánchez, Jesús Moradell, Juan V. Alegre-Requena, Raquel P. Herrera, M. Concepción Gimeno","doi":"10.1039/d6qi00117c","DOIUrl":"https://doi.org/10.1039/d6qi00117c","url":null,"abstract":"We report an unprecedented gold(III)-templated insertion of selenium and tellurium into Au–P bonds of bis(diphenylphosphane)methane (dppm), affording the first examples of κ²-(E,P) Au(III) metallacycles (E = Se, Te) via direct chalcogen transfer under mild conditions. This transformation represents a rare case of heavy-chalcogen incorporation into a metal–phosphorus bond, providing synthetic access to previously elusive Te-functional diphosphanes and extending to their selenium congeners. Structural, spectroscopic, and computational analyses reveal that Au coordination modulates P–E covalency and charge distribution, yielding electronically diverse chalcogenated frameworks. Beyond synthetic novelty, these Au–E–P scaffolds act as potent chalcogen-bond (ChB) donors in transfer hydrogenation, with Te complexes outperforming their Se analogues in line with deeper, more accessible Te σ-holes. Remarkably, their catalytic efficiency parallels that of metal-free phosphonium chalcogenides, prepared by direct methylation of (<em><small><sup>i</sup></small></em>Pr)₃P=E for comparative evaluation. The synergy between Au coordination and chalcogen identity furnishes direct access to otherwise inaccessible Te-functional diphosphanes and establishes a modular platform for tuning σ-hole interactions, advancing the design of main-group/transition-metal hybrids for noncovalent catalysis and molecular materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"45 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471110","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 elegant chemical modification of o-vanillin hydrazide simultaneously produces two hydrazone-based Z/E-isomers, HL-Z and HL-E, where HL-Z = ethyl (Z)-2-(2-(2-hydroxy-3-methoxybenzoyl)hydrazono)-2-(pyridin-2-yl)acetateethyl and HL-E = (E)-2-(2-(2-hydroxy-3-methoxybenzoyl)hydrazono)-2-(pyridin-2-yl)acetate, which can be separated by column chromatography. Their structures are determined by NMR spectra and SC-XRD analysis. Upon irradiation at 365 nm, HL-Z converted unidirectionally into HL-E with the E/Z ratio of 35:65. This isomerization process is thermally irreversible, i.e. HL-E retaining its configuration at heating. The self-assembly of Dy(SCN)3•6H2O with HL-E or HL-Z affords two distinct complexes, one is Dy(III)-based triangle Dy3 ([Dy3(μ3-OH)2(L-E)3(EtOH)2(SCN)4]) and the other is dinuclear Dy2 ([Dy2(HL-Z)(L-Z)2(SCN)2]). Magnetic investigations reveal that Dy2 behaves as a field-induced single-molecule magnet (SMM) with Ueff of ca. 39 K under 400 Oe dc field while Dy3 exhibits typical single-molecule toroic (SMT) properties.
{"title":"Separation of o-vanillin hydrazone isomers constructing Dy2 single-molecule magnet and Dy3 single-molecule toroic","authors":"Linghao Meng, Xu Ying, Jinjiang Wu, Zhenhua Zhu, Xiao-Lei Li, Yunquan Wang, Peng Zhang, Jinkui Tang","doi":"10.1039/d6qi00257a","DOIUrl":"https://doi.org/10.1039/d6qi00257a","url":null,"abstract":"The elegant chemical modification of o-vanillin hydrazide simultaneously produces two hydrazone-based Z/E-isomers, HL-Z and HL-E, where HL-Z = ethyl (Z)-2-(2-(2-hydroxy-3-methoxybenzoyl)hydrazono)-2-(pyridin-2-yl)acetateethyl and HL-E = (E)-2-(2-(2-hydroxy-3-methoxybenzoyl)hydrazono)-2-(pyridin-2-yl)acetate, which can be separated by column chromatography. Their structures are determined by NMR spectra and SC-XRD analysis. Upon irradiation at 365 nm, HL-Z converted unidirectionally into HL-E with the E/Z ratio of 35:65. This isomerization process is thermally irreversible, i.e. HL-E retaining its configuration at heating. The self-assembly of Dy(SCN)3•6H2O with HL-E or HL-Z affords two distinct complexes, one is Dy(III)-based triangle Dy3 ([Dy3(μ3-OH)2(L-E)3(EtOH)2(SCN)4]) and the other is dinuclear Dy2 ([Dy2(HL-Z)(L-Z)2(SCN)2]). Magnetic investigations reveal that Dy2 behaves as a field-induced single-molecule magnet (SMM) with Ueff of ca. 39 K under 400 Oe dc field while Dy3 exhibits typical single-molecule toroic (SMT) properties.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478624","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}
Boshko Koloski, Senja Pollak, Sašo Džeroski, Aleksandar Kondinski
Over the past few years, large language models have become technologically ubiquitous and now offer a powerful route to accelerate discoveries in chemistry. In this article, we highlight current impactful applications of large language models in inorganic chemistry-from smart text mining of the inorganic literature through the proposal and discovery of new materials to real-time experimentation. We also discuss ongoing developments and their potential future impact on the field.
{"title":"Digitalisation of Inorganic Chemistry with LLMs","authors":"Boshko Koloski, Senja Pollak, Sašo Džeroski, Aleksandar Kondinski","doi":"10.1039/d6qi00240d","DOIUrl":"https://doi.org/10.1039/d6qi00240d","url":null,"abstract":"Over the past few years, large language models have become technologically ubiquitous and now offer a powerful route to accelerate discoveries in chemistry. In this article, we highlight current impactful applications of large language models in inorganic chemistry-from smart text mining of the inorganic literature through the proposal and discovery of new materials to real-time experimentation. We also discuss ongoing developments and their potential future impact on the field.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"84 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465980","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}
Zhiming Wang, Shiwei Dong, Chuanliang Yang, Jinyi Chen, Wentao Wang, Tao Li, Guoqiang Yang, Zhong Han
The application of lanthanide-based circularly polarized luminescence (CPL) probes in biological systems has long been impeded by a fundamental trade-off: the need for high-energy ultraviolet excitation to overcome the low absorptivity of f-f transitions versus the phototoxicity and poor tissue penetration inherent to UV irradiation. Herein, we resolve this "excitation bottleneck" by engineering a heteronuclear Ir(III)-Eu(III) dyad that functions as a highly efficient, visible-light-harvesting CPL generator. By exploiting the broad metal-to-ligand charge transfer (MLCT) absorption of a cyclometalated Ir(III) antenna, we successfully red-shift the excitation window to the benign visible region (λex > 425 nm), extending up to ∼500 nm. This sensitization strategy yields intense red Eu(III)-based emission with a substantial luminescence dissymmetry factor (|glum| = 0.114) without requiring deleterious UV light. Capitalizing on this visible-light accessibility and the kinetic inertness of the rigid DO3A scaffold, we demonstrate dual-modal one-and two-photon confocal imaging in living cells. Furthermore, the dyad exhibits efficient singlet oxygen generation (Φ∆ = 0.82), enabling photodynamic therapy. This work establishes a versatile paradigm for visible-light-driven lanthanide chiroptics, effectively bridging the gap between superior chiral photophysical properties and biocompatible excitation requirements.
{"title":"Breaking the Excitation Barrier: Visible-Light-Harvesting Ir(III)-Eu(III) Dyads for Circularly Polarized Luminescence and Theranostics","authors":"Zhiming Wang, Shiwei Dong, Chuanliang Yang, Jinyi Chen, Wentao Wang, Tao Li, Guoqiang Yang, Zhong Han","doi":"10.1039/d5qi02548f","DOIUrl":"https://doi.org/10.1039/d5qi02548f","url":null,"abstract":"The application of lanthanide-based circularly polarized luminescence (CPL) probes in biological systems has long been impeded by a fundamental trade-off: the need for high-energy ultraviolet excitation to overcome the low absorptivity of f-f transitions versus the phototoxicity and poor tissue penetration inherent to UV irradiation. Herein, we resolve this \"excitation bottleneck\" by engineering a heteronuclear Ir(III)-Eu(III) dyad that functions as a highly efficient, visible-light-harvesting CPL generator. By exploiting the broad metal-to-ligand charge transfer (MLCT) absorption of a cyclometalated Ir(III) antenna, we successfully red-shift the excitation window to the benign visible region (λex > 425 nm), extending up to ∼500 nm. This sensitization strategy yields intense red Eu(III)-based emission with a substantial luminescence dissymmetry factor (|glum| = 0.114) without requiring deleterious UV light. Capitalizing on this visible-light accessibility and the kinetic inertness of the rigid DO3A scaffold, we demonstrate dual-modal one-and two-photon confocal imaging in living cells. Furthermore, the dyad exhibits efficient singlet oxygen generation (Φ∆ = 0.82), enabling photodynamic therapy. This work establishes a versatile paradigm for visible-light-driven lanthanide chiroptics, effectively bridging the gap between superior chiral photophysical properties and biocompatible excitation requirements.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466158","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}
Ruru Xu, Xinghua Zhang, Douglas W. Stephan, Yile Wu, Ting Chen, Zhou He, Weili Yan
A novel α-diimine aluminum hydride, LAl(thf)H (L = [(2,6-i Pr2C6H3)NC(Me)]2), which exhibits versatile reactivity with various unsaturated substrates, including imines, hydrazine, azobenzene, aldehydes, and ketones. In these reactions, LAl(thf)H acts either as a hydride donor, hydrogen atom donor, and an electron donor, promoting corresponding dehydrocoupling, hydroalumination, and proton-coupled electron transfer (PCET) reactions. These results represent a new cooperative interactions with α-diimine ligands, which endows it with significant redox activity and provides a platform for studying metal-ligand cooperative electron transfer processes.
{"title":"Diimine-Supported Aluminum Hydride: A Versatile Hydride, Hydrogen Atom and Electron Donor †","authors":"Ruru Xu, Xinghua Zhang, Douglas W. Stephan, Yile Wu, Ting Chen, Zhou He, Weili Yan","doi":"10.1039/d6qi00295a","DOIUrl":"https://doi.org/10.1039/d6qi00295a","url":null,"abstract":"A novel α-diimine aluminum hydride, LAl(thf)H (L = [(2,6-i Pr2C6H3)NC(Me)]2), which exhibits versatile reactivity with various unsaturated substrates, including imines, hydrazine, azobenzene, aldehydes, and ketones. In these reactions, LAl(thf)H acts either as a hydride donor, hydrogen atom donor, and an electron donor, promoting corresponding dehydrocoupling, hydroalumination, and proton-coupled electron transfer (PCET) reactions. These results represent a new cooperative interactions with α-diimine ligands, which endows it with significant redox activity and provides a platform for studying metal-ligand cooperative electron transfer processes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471111","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}
Zhanyao Xu, Sajid Ur Rehman, Yuan Xu, Haris Habib, Zeeshan Tariq, Hafiz Muhammad Naeem Ullah, Yang Wang, Chuanbo Li, Xiaoming Zhang
The development of efficient photocatalytic systems capable of harvesting visible light is essential for sustainable water splitting and addressing the escalating environmental and energy crises. In this study, first-principles calculations are employed to design and evaluate two-dimensional (2D) pentagonal MgX2 (X = O, S, Se, Te) monolayers for photocatalytic water splitting and CO2 reduction. The structural integrity and stability of these materials are confirmed through formation energy analysis, phonon dispersion, ab initio molecular dynamics simulations, and elastic constant evaluations. Hybrid HSE06 functional calculations predict band gaps ranging from 1.488 to 4.471 eV, with penta-MgO2 exhibiting a direct band gap, while the others possess indirect band gaps. All monolayers exhibit suitable band edge alignments for driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), as well as for facilitating CO2 reduction. Moreover, they exhibit high carrier mobilities and strong optical absorption in the UV–visible region, with absorption coefficients exceeding 105 cm−1. Gibbs free energy calculations confirm the thermodynamic viability of water splitting under the applied external potential. Notably, penta-MgTe2 emerges as the most promising photocatalyst for CO2 reduction due to its efficient stabilization of key intermediates (*CHO and *CH3OH) and low-energy hydrogenation steps, favoring selective CH4 production under solar-driven conditions. These findings highlight the potential of pentagonal Mg-based 2D materials as efficient and sustainable photocatalysts for clean energy conversion applications.
{"title":"Novel pentagonal MgX2 (X = O, S, Se, Te) monolayers: promising photocatalysts for overall water splitting and CO2 reduction","authors":"Zhanyao Xu, Sajid Ur Rehman, Yuan Xu, Haris Habib, Zeeshan Tariq, Hafiz Muhammad Naeem Ullah, Yang Wang, Chuanbo Li, Xiaoming Zhang","doi":"10.1039/d5qi02524a","DOIUrl":"https://doi.org/10.1039/d5qi02524a","url":null,"abstract":"The development of efficient photocatalytic systems capable of harvesting visible light is essential for sustainable water splitting and addressing the escalating environmental and energy crises. In this study, first-principles calculations are employed to design and evaluate two-dimensional (2D) pentagonal MgX<small><sub>2</sub></small> (X = O, S, Se, Te) monolayers for photocatalytic water splitting and CO<small><sub>2</sub></small> reduction. The structural integrity and stability of these materials are confirmed through formation energy analysis, phonon dispersion, <em>ab initio</em> molecular dynamics simulations, and elastic constant evaluations. Hybrid HSE06 functional calculations predict band gaps ranging from 1.488 to 4.471 eV, with penta-MgO<small><sub>2</sub></small> exhibiting a direct band gap, while the others possess indirect band gaps. All monolayers exhibit suitable band edge alignments for driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), as well as for facilitating CO<small><sub>2</sub></small> reduction. Moreover, they exhibit high carrier mobilities and strong optical absorption in the UV–visible region, with absorption coefficients exceeding 10<small><sup>5</sup></small> cm<small><sup>−1</sup></small>. Gibbs free energy calculations confirm the thermodynamic viability of water splitting under the applied external potential. Notably, penta-MgTe<small><sub>2</sub></small> emerges as the most promising photocatalyst for CO<small><sub>2</sub></small> reduction due to its efficient stabilization of key intermediates (*CHO and *CH<small><sub>3</sub></small>OH) and low-energy hydrogenation steps, favoring selective CH<small><sub>4</sub></small> production under solar-driven conditions. These findings highlight the potential of pentagonal Mg-based 2D materials as efficient and sustainable photocatalysts for clean energy conversion applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466157","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 integration of organic stimuli-responsive groups with electrochemically active metal ions offers a promising strategy for developing novel high-sensitivity photodetectors and other multifunctional materials. Herein, a new magnesium-based pyridinium complex, [Mg(cbby)(H₂O)₅]•DMF (1), was successfully synthesized and comprehensively characterized. Complex 1 exhibits intriguing photochromic and thermochromic behaviors, transitioning from colorless to light black under UV light (365 nm) and to light yellow upon heating (150 °C). Remarkably, the thermally treated phase (1T) demonstrates a significantly accelerated photoresponse, with its photochromic rate constant being 1.68 times faster than that of the pristine sample, attributed to a thermally modified, more efficient electron-transfer pathway. Furthermore, complex 1 demonstrates pronounced photoelectrochemical activity with a high on/off current ratio of 35 under xenon lamp irradiation, underscoring its potential in light-harvesting. The complex 1 also functions as a highly sensitive and selective fluorescent sensor for detecting trace water in organic solvents (MeCN, DMF) with low detection limits (~0.03% v/v). Leveraging its reversible optical switching and tunable fluorescence, proof-of-concept applications in multi-level anti-counterfeiting, rewritable media, and information encryption are successfully demonstrated. This work highlights the great potential of synergistically combining the unique properties of magnesium and photoresponsive pyridinium ligands to create advanced smart materials.
{"title":"A Multistimuli-Responsive Chromic Magnesium-Pyridinium Complex for Trace Water Detection, Switchable Photocurrent and Advanced Anti-Counterfeiting.","authors":"Dong-Dong Yang, Jian-Hua Xue, Ze-Liang Zhang, Zhenglin Chen, Yuan-Yuan Zuo, Rui-Chang Tian, Hanwen Zheng, Xiangjun Zheng","doi":"10.1039/d6qi00001k","DOIUrl":"https://doi.org/10.1039/d6qi00001k","url":null,"abstract":"The integration of organic stimuli-responsive groups with electrochemically active metal ions offers a promising strategy for developing novel high-sensitivity photodetectors and other multifunctional materials. Herein, a new magnesium-based pyridinium complex, [Mg(cbby)(H₂O)₅]•DMF (1), was successfully synthesized and comprehensively characterized. Complex 1 exhibits intriguing photochromic and thermochromic behaviors, transitioning from colorless to light black under UV light (365 nm) and to light yellow upon heating (150 °C). Remarkably, the thermally treated phase (1T) demonstrates a significantly accelerated photoresponse, with its photochromic rate constant being 1.68 times faster than that of the pristine sample, attributed to a thermally modified, more efficient electron-transfer pathway. Furthermore, complex 1 demonstrates pronounced photoelectrochemical activity with a high on/off current ratio of 35 under xenon lamp irradiation, underscoring its potential in light-harvesting. The complex 1 also functions as a highly sensitive and selective fluorescent sensor for detecting trace water in organic solvents (MeCN, DMF) with low detection limits (~0.03% v/v). Leveraging its reversible optical switching and tunable fluorescence, proof-of-concept applications in multi-level anti-counterfeiting, rewritable media, and information encryption are successfully demonstrated. This work highlights the great potential of synergistically combining the unique properties of magnesium and photoresponsive pyridinium ligands to create advanced smart materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147465915","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 direct correlation between chirality and second-harmonic generation (SHG) remains underexplored in nonlinear optical (NLO) materials. Herein, we report a pair of dextroisomer and enantiomer crystals, 4-nitro-D-phenylalanine nitrate, (D-NPA, P212121) and its racemate rac-4-nitro-phenylalanine nitrate (rac-NPA, P21/c). D-NPA exhibits excellent SHG performance (2.8 × KDP) and a large birefringence (Δnobv. = 0.131), while rac-NPA is SHG inactive. This pair directly demonstrates that the chirality plays a decisive role in the formation of NCS structure and SHG properties. Theoretical calculations indicate that the SHG primarily originates from the benzene rings and nitro groups in the organic component, their contribution rates are 56% and 47% respectively, and the large birefringence is closely related to the parallel alignment of the NO3 -groups.
在非线性光学（NLO）材料中，手性与二次谐波产生（SHG）之间的直接关系尚未得到充分的研究。在此，我们报道了一对右旋异构体和对映体晶体，4-硝基- d -苯丙氨酸硝酸，（D-NPA, P212121）和它的外消旋物rac-4-硝基-苯丙氨酸硝酸（rac-NPA, P21/c）。D-NPA具有优异的SHG性能（2.8 × KDP）和大双折射（Δnobv）。= 0.131)，而rac-NPA对SHG无活性。这对直接证明了手性在NCS结构的形成和SHG性质中起决定性作用。理论计算表明，SHG主要来源于有机组分中的苯环和硝基，其贡献率分别为56%和47%，且大双折射与NO3 -基团的平行排列密切相关。
{"title":"Chirality-Induced Second Harmonic Generation in Supramolecular 4-Nitro-D-Phenylalanine Hybrid Crystal","authors":"Ye Tan, Qing-Ju Gao, Wen-Shuang Mu, Xing-Guo Xiang, Gao-Yu Zhao, Jing-Yu Guo, Zhihua Yang, Ling Chen","doi":"10.1039/d6qi00217j","DOIUrl":"https://doi.org/10.1039/d6qi00217j","url":null,"abstract":"The direct correlation between chirality and second-harmonic generation (SHG) remains underexplored in nonlinear optical (NLO) materials. Herein, we report a pair of dextroisomer and enantiomer crystals, 4-nitro-D-phenylalanine nitrate, (D-NPA, P212121) and its racemate rac-4-nitro-phenylalanine nitrate (rac-NPA, P21/c). D-NPA exhibits excellent SHG performance (2.8 × KDP) and a large birefringence (Δnobv. = 0.131), while rac-NPA is SHG inactive. This pair directly demonstrates that the chirality plays a decisive role in the formation of NCS structure and SHG properties. Theoretical calculations indicate that the SHG primarily originates from the benzene rings and nitro groups in the organic component, their contribution rates are 56% and 47% respectively, and the large birefringence is closely related to the parallel alignment of the NO3 -groups.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439692","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}
Xylene poses a threat to environmental and public health due to its neurotoxicity and strong irritancy, necessitating the development of efficient trace detection technologies. However, existing metal oxide semiconductor-based xylene sensors tend to have drawbacks such as high detection limits, insufficient response, poor humidity resistance, and susceptibility to cross-interference from aromatic compounds. In this study, Mo-doped nickel oxide nanofibers with varying doping ratios were fabricated by combining a facile electrospinning process with thermal treatment, and their gas-sensing properties were systematically evaluated. The results demonstrate that the sensor with a Mo doping concentration of 12.5 at% exhibited the maximum response to 20 ppm xylene at 265 °C (S ≈ 120.9), an ultra-low detection limit of 20 ppb, excellent selectivity, outstanding humidity resistance, and long-term stability. The improvement in sensing performance primarily stems from the modulation of valence state distribution in nickel oxide by aliovalent molybdenum doping. This process improves charge transfer efficiency and increases oxygen vacancy concentration. Additionally, the incorporation of Mo significantly enlarges the specific surface area and increases the quantity of micropores and mesopores. These factors collectively optimize the activity of surface chemisorbed oxygen, thereby markedly improving gas-sensing reaction efficiency. In situ Fourier transform infrared analysis reveals the surface oxidation reaction process and final reaction products of xylene. This work provides a feasible material strategy for developing high-performance xylene gas sensors, demonstrating promising potential for applications in trace xylene detection.
{"title":"Oxygen vacancy engineering via Mo doping in NiO nanofibers for selective trace xylene detection","authors":"Xiaowen Zhang, Qi Lei, Lixiang Wang, Qingge Feng, Qihua Liang","doi":"10.1039/d6qi00031b","DOIUrl":"https://doi.org/10.1039/d6qi00031b","url":null,"abstract":"Xylene poses a threat to environmental and public health due to its neurotoxicity and strong irritancy, necessitating the development of efficient trace detection technologies. However, existing metal oxide semiconductor-based xylene sensors tend to have drawbacks such as high detection limits, insufficient response, poor humidity resistance, and susceptibility to cross-interference from aromatic compounds. In this study, Mo-doped nickel oxide nanofibers with varying doping ratios were fabricated by combining a facile electrospinning process with thermal treatment, and their gas-sensing properties were systematically evaluated. The results demonstrate that the sensor with a Mo doping concentration of 12.5 at% exhibited the maximum response to 20 ppm xylene at 265 °C (<em>S</em> ≈ 120.9), an ultra-low detection limit of 20 ppb, excellent selectivity, outstanding humidity resistance, and long-term stability. The improvement in sensing performance primarily stems from the modulation of valence state distribution in nickel oxide by aliovalent molybdenum doping. This process improves charge transfer efficiency and increases oxygen vacancy concentration. Additionally, the incorporation of Mo significantly enlarges the specific surface area and increases the quantity of micropores and mesopores. These factors collectively optimize the activity of surface chemisorbed oxygen, thereby markedly improving gas-sensing reaction efficiency. <em>In situ</em> Fourier transform infrared analysis reveals the surface oxidation reaction process and final reaction products of xylene. This work provides a feasible material strategy for developing high-performance xylene gas sensors, demonstrating promising potential for applications in trace xylene detection.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147439689","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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