Self-assembled architectures of NiF2 nanoparticles, which were obtained from the thermal decomposition of NiF2·4H2O, have performed better as conversion-type cathode materials for lithium-ion batteries. However, due to the lack of systematic insight into the microstructural and morphological evolution of NiF2·4H2O, inconsistencies have always existed in its decomposition temperature and pathway. Furthermore, nanoscale NiF2·4H2O has never been considered in such studies, let alone its self-assembled architectures and their comparison with bulk counterparts. Additionally, as an interesting thermochemical material, NiF2·4H2O lacks experimental evaluation. Here, we present these aspects of self-assembled NiF2·4H2O architectures and evaluate the nanostructuring effect on their dehydration mechanism and thermal energy storage capacity. Marked differences were found between the decomposition temperature and mechanism of nano- and bulk NiF2·4H2O. Both samples decomposed in two irreversible steps, which involved mostly the loss of water, giving the end product t-NiF2-x(OH)x. However, the two samples followed different decomposition pathways. Nano NiF2·4H2O converted directly to t-NiF2-x(OH)x, while the diaspore form of o-NiF2-x(OH)x was found as an intermediate phase in the case of the bulk sample. Furthermore, the thermal energy storage capacity of nanoscale NiF2·4H2O was not only larger than that of the bulk but was also comparable to that of other top-performing thermochemical materials.
{"title":"Influence of Nanostructuring on the Dehydration Mechanism of NiF2·4H2O: Structural, Thermal, and Kinetic Studies.","authors":"Hameed Ullah,Nicolas Batisse,Pierre Carrère,Kévin Lemoine,Yohann Coulier,Xin Jiang,Pierre Bonnet","doi":"10.1021/acs.inorgchem.5c05949","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05949","url":null,"abstract":"Self-assembled architectures of NiF2 nanoparticles, which were obtained from the thermal decomposition of NiF2·4H2O, have performed better as conversion-type cathode materials for lithium-ion batteries. However, due to the lack of systematic insight into the microstructural and morphological evolution of NiF2·4H2O, inconsistencies have always existed in its decomposition temperature and pathway. Furthermore, nanoscale NiF2·4H2O has never been considered in such studies, let alone its self-assembled architectures and their comparison with bulk counterparts. Additionally, as an interesting thermochemical material, NiF2·4H2O lacks experimental evaluation. Here, we present these aspects of self-assembled NiF2·4H2O architectures and evaluate the nanostructuring effect on their dehydration mechanism and thermal energy storage capacity. Marked differences were found between the decomposition temperature and mechanism of nano- and bulk NiF2·4H2O. Both samples decomposed in two irreversible steps, which involved mostly the loss of water, giving the end product t-NiF2-x(OH)x. However, the two samples followed different decomposition pathways. Nano NiF2·4H2O converted directly to t-NiF2-x(OH)x, while the diaspore form of o-NiF2-x(OH)x was found as an intermediate phase in the case of the bulk sample. Furthermore, the thermal energy storage capacity of nanoscale NiF2·4H2O was not only larger than that of the bulk but was also comparable to that of other top-performing thermochemical materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"16 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-23DOI: 10.1021/acs.inorgchem.5c04479
Surendar Karwasara,Xiang Ma,Hatem M A Amin,Timo Fockenberg,Gaurav Kanu,Christoph Wölper,Sabrina Disch,Stephan Schulz
A series of mixed-valent, multinuclear cobalt-oxido clusters [CoIIICoII2(mdea)3(H2mdea)]ClO4 (1), [CoIII2CoII2(mdea)4(DAA)2](BPh4)2 (2), [CoIII3CoII4(mdea)6(NO3)3](NO3)2 (3), [CoIII3CoII4(mdea)6(fa)3](ClO4)2 (4), [Na2CoIII4CoII4(mdea)6(CO3)4(OH)2(H2O)2] (5), [CoIII3CoII7(mdea)6(fa)5(OH)4](ClO4)3 (6), and [CoIII4CoII9(mdea)8(NO3)4(OH)8](NO3)2 (7) containing up to 13 Co atoms were synthesized and structurally characterized using single-crystal X-ray diffraction as well as FT-IR and UV-vis spectroscopy. The cobalt-oxido clusters contain N-methyldiethanolamine (H2mdea) as a stabilizing ligand and feature Co3O4 (1), Co4O6 (2), Co7O12 (3, 4), Na2Co8O18 (M10O18) (5), Co10O16 (6), and Co13O24 (7) scaffolds. The increasing number of Co cations in the cobalt-oxido cores of compounds 1-7 results from the systematic addition of pseudocubane Co3O4 units and the progressive incorporation of hydroxide ligands. The water oxidation activity and electrochemical properties of the CoII/CoIII centers in the complexes were studied by cyclic voltammetry (CV), while their magnetic properties were investigated via temperature-dependent magnetic susceptibility.
{"title":"Multinuclear Mixed-Valent Co-Oxido Complexes: Synthesis, Structure, Magnetic, and Electrochemical Properties.","authors":"Surendar Karwasara,Xiang Ma,Hatem M A Amin,Timo Fockenberg,Gaurav Kanu,Christoph Wölper,Sabrina Disch,Stephan Schulz","doi":"10.1021/acs.inorgchem.5c04479","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04479","url":null,"abstract":"A series of mixed-valent, multinuclear cobalt-oxido clusters [CoIIICoII2(mdea)3(H2mdea)]ClO4 (1), [CoIII2CoII2(mdea)4(DAA)2](BPh4)2 (2), [CoIII3CoII4(mdea)6(NO3)3](NO3)2 (3), [CoIII3CoII4(mdea)6(fa)3](ClO4)2 (4), [Na2CoIII4CoII4(mdea)6(CO3)4(OH)2(H2O)2] (5), [CoIII3CoII7(mdea)6(fa)5(OH)4](ClO4)3 (6), and [CoIII4CoII9(mdea)8(NO3)4(OH)8](NO3)2 (7) containing up to 13 Co atoms were synthesized and structurally characterized using single-crystal X-ray diffraction as well as FT-IR and UV-vis spectroscopy. The cobalt-oxido clusters contain N-methyldiethanolamine (H2mdea) as a stabilizing ligand and feature Co3O4 (1), Co4O6 (2), Co7O12 (3, 4), Na2Co8O18 (M10O18) (5), Co10O16 (6), and Co13O24 (7) scaffolds. The increasing number of Co cations in the cobalt-oxido cores of compounds 1-7 results from the systematic addition of pseudocubane Co3O4 units and the progressive incorporation of hydroxide ligands. The water oxidation activity and electrochemical properties of the CoII/CoIII centers in the complexes were studied by cyclic voltammetry (CV), while their magnetic properties were investigated via temperature-dependent magnetic susceptibility.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"146 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502497","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-23DOI: 10.1021/acs.inorgchem.6c01063
Xin Lu,Dongju Zhang
A recently developed transformation merges features of Suzuki-Miyaura and Buchwald-Hartwig couplings by introducing formal nitrene insertion, thereby redirecting the reaction outcome from C-C-linked biaryls to C-N-C-linked diarylamines (Science, 2024, 383, 1019). In this work, density functional theory (DFT) calculations are employed to elucidate the reaction mechanism and the ligand-controlled origin of the selectivity. The results clarify that the reaction proceeds via a nucleophile-first pathway rather than an electrophile-first pathway, resolving a key mechanistic ambiguity left open by the experimental study. Moreover, the calculations highlight the pivotal role of the ligand in governing product selectivity. The t-BuBrettPhos ligand stabilizes the C-N bond-forming transition state via C-H···π interactions with the substrate, favoring diarylamine formation. In contrast, the RuPhos ligand promotes C-C bond formation due to its intrinsically reduced steric bulk and electron-deficient nature, leading to the biphenyl product. These findings offer molecular-level insights into the elegant aminative Suzuki-Miyaura coupling strategy and its ligand-controlled pathway selectivity, providing a theoretical foundation for the rational design of catalysts with improved efficiency.
最近开发的一种转化结合了Suzuki-Miyaura和Buchwald-Hartwig偶联的特征，通过引入正式的亚硝基插入，从而将反应结果从c - c连接的双芳基转向c - n - c连接的二芳胺（Science, 2024, 383, 1019）。本研究采用密度泛函理论（DFT）计算来阐明反应机理和配体控制的选择性来源。结果表明，反应是通过亲核优先途径进行的，而不是亲电优先途径，解决了实验研究遗留的关键机制歧义。此外，计算强调了配体在控制产物选择性中的关键作用。t-BuBrettPhos配体通过C-H··π与底物的相互作用稳定了C-N键形成的过渡态，有利于二芳胺的形成。相比之下，RuPhos配体由于其本质上减少的空间体积和缺电子的性质，促进了C-C键的形成，导致联苯产物。这些发现从分子水平上深入了解了优雅的胺基Suzuki-Miyaura偶联策略及其配体控制的途径选择性，为合理设计具有更高效率的催化剂提供了理论基础。
{"title":"DFT Insights into Pd-Catalyzed Aminative Suzuki-Miyaura Coupling for Diarylamine Synthesis.","authors":"Xin Lu,Dongju Zhang","doi":"10.1021/acs.inorgchem.6c01063","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c01063","url":null,"abstract":"A recently developed transformation merges features of Suzuki-Miyaura and Buchwald-Hartwig couplings by introducing formal nitrene insertion, thereby redirecting the reaction outcome from C-C-linked biaryls to C-N-C-linked diarylamines (Science, 2024, 383, 1019). In this work, density functional theory (DFT) calculations are employed to elucidate the reaction mechanism and the ligand-controlled origin of the selectivity. The results clarify that the reaction proceeds via a nucleophile-first pathway rather than an electrophile-first pathway, resolving a key mechanistic ambiguity left open by the experimental study. Moreover, the calculations highlight the pivotal role of the ligand in governing product selectivity. The t-BuBrettPhos ligand stabilizes the C-N bond-forming transition state via C-H···π interactions with the substrate, favoring diarylamine formation. In contrast, the RuPhos ligand promotes C-C bond formation due to its intrinsically reduced steric bulk and electron-deficient nature, leading to the biphenyl product. These findings offer molecular-level insights into the elegant aminative Suzuki-Miyaura coupling strategy and its ligand-controlled pathway selectivity, providing a theoretical foundation for the rational design of catalysts with improved efficiency.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-23DOI: 10.1021/acs.inorgchem.5c05829
Ziyu Hu,Chenyang Li
The accurate prediction of magnetic exchange coupling constants (J) in transition-metal complexes remains challenging for the electronic-structure theory. In this work, we demonstrate that the state-average driven similarity renormalization group second-order perturbation theory (SA-DSRG-PT2), combined with the density matrix renormalization group, provides quantitative J values on a set of 21 3d bimetallic complexes with a focus on dicopper species. Active orbitals are systematically identified using the atomic valence active space approach, ensuring a consistent inclusion of metal 3d and 4d shells and the ligand orbitals involved in superexchange pathways. Analysis of the SA-DSRG-PT2 effective Hamiltonians indicates that the reduction of the on-site Coulomb repulsion is the primary origin of the improved exchange couplings. In addition, we adopt the orbital mutual correlation plot as an intuitive tool to visualize exchange pathways, allowing direct identifications of metal-metal and metal-ligand correlations and their modulation by dynamical correlation. These results establish SA-DSRG-PT2 as a robust and practical multireference approach for studying magnetic interactions in transition-metal complexes.
{"title":"Toward Quantitative Computations of Exchange Coupling Constants in Transition-Metal Complexes via Multireference Driven Similarity Renormalization Group.","authors":"Ziyu Hu,Chenyang Li","doi":"10.1021/acs.inorgchem.5c05829","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05829","url":null,"abstract":"The accurate prediction of magnetic exchange coupling constants (J) in transition-metal complexes remains challenging for the electronic-structure theory. In this work, we demonstrate that the state-average driven similarity renormalization group second-order perturbation theory (SA-DSRG-PT2), combined with the density matrix renormalization group, provides quantitative J values on a set of 21 3d bimetallic complexes with a focus on dicopper species. Active orbitals are systematically identified using the atomic valence active space approach, ensuring a consistent inclusion of metal 3d and 4d shells and the ligand orbitals involved in superexchange pathways. Analysis of the SA-DSRG-PT2 effective Hamiltonians indicates that the reduction of the on-site Coulomb repulsion is the primary origin of the improved exchange couplings. In addition, we adopt the orbital mutual correlation plot as an intuitive tool to visualize exchange pathways, allowing direct identifications of metal-metal and metal-ligand correlations and their modulation by dynamical correlation. These results establish SA-DSRG-PT2 as a robust and practical multireference approach for studying magnetic interactions in transition-metal complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147502517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-21DOI: 10.1021/acs.inorgchem.6c00400
Medet Segizbayev, Jonathan Choong, Anton Dmitrienko, Georgii I. Nikonov
Reduction of cationic stannylene [(dim(NHC))SnCl]+ (dim(NHC) = diimino N-heterocyclic carbene) by potassium graphite affords the Sn(0) compound (stannylone) (dim(NHC))Sn (14). SC-XRD study of 14 revealed a shortened C–Sn bond, indicating a multiple bond character. Stannylone 14 undergoes a [2 + 2] cycloaddition with isocyanates RNCO (R = 4-tolyl or 2,6-xylyl) to furnish novel alkyl carboxamido stannylenes 21 (R = 4-tolyl) and 22 (R = 2,6-xylyl), featuring a C–C bond between the former carbene carbon and the isocyanate moiety. Heating a mixture of 22 with 4-tolyl isocyanate to 100 °C results in isocyanate metathesis, demonstrating reversible C–C bond formation in the coordination sphere of the tin atom.
{"title":"Diimino(NHC)-Stabilized Stannylone: Synthesis and Reversible Coupling with Isocyanates","authors":"Medet Segizbayev, Jonathan Choong, Anton Dmitrienko, Georgii I. Nikonov","doi":"10.1021/acs.inorgchem.6c00400","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00400","url":null,"abstract":"Reduction of cationic stannylene [(dim(NHC))SnCl]<sup>+</sup> (dim(NHC) = diimino N-heterocyclic carbene) by potassium graphite affords the Sn(0) compound (stannylone) (dim(NHC))Sn (<b>14</b>). SC-XRD study of <b>14</b> revealed a shortened C–Sn bond, indicating a multiple bond character. Stannylone <b>14</b> undergoes a [2 + 2] cycloaddition with isocyanates RNCO (R = 4-tolyl or 2,6-xylyl) to furnish novel alkyl carboxamido stannylenes <b>21</b> (R = 4-tolyl) and <b>22</b> (R = 2,6-xylyl), featuring a C–C bond between the former carbene carbon and the isocyanate moiety. Heating a mixture of <b>22</b> with 4-tolyl isocyanate to 100 °C results in isocyanate metathesis, demonstrating reversible C–C bond formation in the coordination sphere of the tin atom.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492594","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-21DOI: 10.1021/acs.inorgchem.6c00457
Sisi Zhan, Jun Xu, Xiaoming Liu, Yanqing Li, Qi Yuan, Jun Lin
In this work, a series of Eu2+-doped SrLa2Sc2O7 phosphors were rationally designed and synthesized, exhibiting high photoluminescence quantum yields and excellent thermal stability. Under 440 nm blue-light excitation, these phosphors show a broad red emission band centered at 613 nm, with a full width at half-maximum (fwhm) of 81 nm (corresponding to ∼0.26 eV at ∼613 nm). By employing a Sr2+/Ba2+ substitution strategy to modulate the local crystal field around Eu2+, both a redshift in the emission peak and significant spectral broadening were achieved. Notably, complete substitution of Sr2+ with Ba2+ yielded a BaLa2Sc1.985O7:0.015Eu2+ phosphor that exhibits a broadband near-infrared (NIR) emission peaking at 812 nm with an ultrabroad fwhm of 318 nm (corresponding to ∼0.59 eV at ∼812 nm). Moreover, aliovalent substitution of Eu2+ for Sc3+ generates oxygen-vacancy-related defect centers that act as carrier traps, extending the emission lifetime and enhancing resistance to thermal quenching in SrLa2Sc1.985O7:0.015Eu2+. In addition, incorporation of larger Ba2+ ions softens the host lattice, strengthening excited-state lattice relaxation and electron–phonon coupling, thereby increasing the Stokes shift and further broadening the Eu2+ emission band to realize tunable broadband red-to-NIR emission in Eu2+-activated Sr1–xBaxLa2Sc2O7 phosphors. These findings broaden the family of Eu2+-activated scandate oxide phosphors and provide a viable strategy for tuning broadband NIR emission via targeted cation substitution devices.
{"title":"Tunable Broadband Red-To-Near-Infrared Emission in Eu2+-Activated Sr1–xBaxLa2Sc2O7 Phosphors via Site-Selective Occupation and Cation Substitution","authors":"Sisi Zhan, Jun Xu, Xiaoming Liu, Yanqing Li, Qi Yuan, Jun Lin","doi":"10.1021/acs.inorgchem.6c00457","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00457","url":null,"abstract":"In this work, a series of Eu<sup>2+</sup>-doped SrLa<sub>2</sub>Sc<sub>2</sub>O<sub>7</sub> phosphors were rationally designed and synthesized, exhibiting high photoluminescence quantum yields and excellent thermal stability. Under 440 nm blue-light excitation, these phosphors show a broad red emission band centered at 613 nm, with a full width at half-maximum (fwhm) of 81 nm (corresponding to ∼0.26 eV at ∼613 nm). By employing a Sr<sup>2+</sup>/Ba<sup>2+</sup> substitution strategy to modulate the local crystal field around Eu<sup>2+</sup>, both a redshift in the emission peak and significant spectral broadening were achieved. Notably, complete substitution of Sr<sup>2+</sup> with Ba<sup>2+</sup> yielded a BaLa<sub>2</sub>Sc<sub>1.985</sub>O<sub>7</sub>:0.015Eu<sup>2+</sup> phosphor that exhibits a broadband near-infrared (NIR) emission peaking at 812 nm with an ultrabroad fwhm of 318 nm (corresponding to ∼0.59 eV at ∼812 nm). Moreover, aliovalent substitution of Eu<sup>2+</sup> for Sc<sup>3+</sup> generates oxygen-vacancy-related defect centers that act as carrier traps, extending the emission lifetime and enhancing resistance to thermal quenching in SrLa<sub>2</sub>Sc<sub>1.985</sub>O<sub>7</sub>:0.015Eu<sup>2+</sup>. In addition, incorporation of larger Ba<sup>2+</sup> ions softens the host lattice, strengthening excited-state lattice relaxation and electron–phonon coupling, thereby increasing the Stokes shift and further broadening the Eu<sup>2+</sup> emission band to realize tunable broadband red-to-NIR emission in Eu<sup>2+</sup>-activated Sr<sub>1–<i>x</i></sub>Ba<sub><i>x</i></sub>La<sub>2</sub>Sc<sub>2</sub>O<sub>7</sub> phosphors. These findings broaden the family of Eu<sup>2+</sup>-activated scandate oxide phosphors and provide a viable strategy for tuning broadband NIR emission via targeted cation substitution devices.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"94 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147492600","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The detection and sensing of amino acids through turn-on and ratiometric fluorescence signals are always challenging due to different shapes, sizes, acidities, basicities, and structural arrangement of amino acids. In general, amino acids are important biomarkers for identifying human health, providing a rapid, sensitive, and easy way to disease prevention and early diagnosis. Considering this, two highly fluorescent nitro-functionalized metal-organic frameworks (MOFs) have been designed using a mixed-ligands strategy, following a slow-diffusion technique. Both the compounds have a two-dimensional structure with the molecular formula {[Zn(4,4'-dps)(5-nip)](solvent)x}n (1) and {[Cd(4,4'-dps)(5-nip)(EtOH)]}n (2) (where 4,4'-dps = 4,4'-dipyridyl sulfide and 5-nip = 5-nitroisophthalate) and have been characterized thoroughly. The desolvated forms of 1 and 2 (1' and 2') are stable in different solvents and also within the wide pH range of 2-12. Interestingly, the fluorescence spectra of 1' and 2' showed photoinduced electron transfer (PET) driven turn-on fluorescence in the presence of tryptophan (Trp) with a low limit of detection. However, both the compounds involved in excited-state intermolecular proton transfer (ESPT) with aspartic acid (Asp), resulting in the selective ratiometric signal in fluorescence behavior. These observations allow the convenient method for the detection of aforesaid amino acids in water, through a diverse fluorescence mechanistic pathway.
{"title":"Widely pH-Stable Fluorescent Metal-Organic Frameworks for Selective Detection of Amino Acids.","authors":"Bidyadhar Mahato,Swapan Saren,Anupam Maiti,Debajyoti Ghoshal","doi":"10.1021/acs.inorgchem.5c05994","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05994","url":null,"abstract":"The detection and sensing of amino acids through turn-on and ratiometric fluorescence signals are always challenging due to different shapes, sizes, acidities, basicities, and structural arrangement of amino acids. In general, amino acids are important biomarkers for identifying human health, providing a rapid, sensitive, and easy way to disease prevention and early diagnosis. Considering this, two highly fluorescent nitro-functionalized metal-organic frameworks (MOFs) have been designed using a mixed-ligands strategy, following a slow-diffusion technique. Both the compounds have a two-dimensional structure with the molecular formula {[Zn(4,4'-dps)(5-nip)](solvent)x}n (1) and {[Cd(4,4'-dps)(5-nip)(EtOH)]}n (2) (where 4,4'-dps = 4,4'-dipyridyl sulfide and 5-nip = 5-nitroisophthalate) and have been characterized thoroughly. The desolvated forms of 1 and 2 (1' and 2') are stable in different solvents and also within the wide pH range of 2-12. Interestingly, the fluorescence spectra of 1' and 2' showed photoinduced electron transfer (PET) driven turn-on fluorescence in the presence of tryptophan (Trp) with a low limit of detection. However, both the compounds involved in excited-state intermolecular proton transfer (ESPT) with aspartic acid (Asp), resulting in the selective ratiometric signal in fluorescence behavior. These observations allow the convenient method for the detection of aforesaid amino acids in water, through a diverse fluorescence mechanistic pathway.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147483672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Due to its high volatility and long half-life, iodine poses a serious threat to the environment and human health. Therefore, trapping radioactive iodine is of significant importance. In this study, a novel uranyl-based metal-organic framework (MOF) material, IHEP-103, was synthesized via a solvothermal process by combining Schiff base ligands with uranyl cations. IHEP-103 features 1D rhombic channels functionalized by dimethylamine, uranyl acyl oxygen atoms, imine nitrogen atoms, aromatic rings, and alkyl hydrogen moieties. The structural characteristics of IHEP-103 (such as its multiple functional groups) give it potential applications in iodine capture, while the dimethylammonium cation further enhances iodine adsorption through electrostatic interactions and intermolecular C-H···I interactions. The results from XPS, Raman spectroscopy, and single-crystal X-ray diffraction reveal an evolution of the iodine species surrounding the dimethylamine group with increasing iodine loading: from the (I2·I3)- supramolecular complex structure to the polyiodide anions I5-.
{"title":"Iodine Capture and Transformation at a Hydrogen-Bond-Stabilized Dimethylammonium Site within a Uranyl-Based MOF.","authors":"Zi-Meng Wang,Jing Liao,Xuan Fu,Zhi-Heng Zhou,Si-Yu Chen,Zhi-Wei Huang,Xiao-Jing Li,Lei Mei,Li-Yong Yuan,Hong-Bin Qi,Wei-Qun Shi,Kong-Qiu Hu","doi":"10.1021/acs.inorgchem.6c00748","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00748","url":null,"abstract":"Due to its high volatility and long half-life, iodine poses a serious threat to the environment and human health. Therefore, trapping radioactive iodine is of significant importance. In this study, a novel uranyl-based metal-organic framework (MOF) material, IHEP-103, was synthesized via a solvothermal process by combining Schiff base ligands with uranyl cations. IHEP-103 features 1D rhombic channels functionalized by dimethylamine, uranyl acyl oxygen atoms, imine nitrogen atoms, aromatic rings, and alkyl hydrogen moieties. The structural characteristics of IHEP-103 (such as its multiple functional groups) give it potential applications in iodine capture, while the dimethylammonium cation further enhances iodine adsorption through electrostatic interactions and intermolecular C-H···I interactions. The results from XPS, Raman spectroscopy, and single-crystal X-ray diffraction reveal an evolution of the iodine species surrounding the dimethylamine group with increasing iodine loading: from the (I2·I3)- supramolecular complex structure to the polyiodide anions I5-.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489861","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-20DOI: 10.1021/acs.inorgchem.6c00080
Qi-Yue Xin,Shuai Liang,Shi-Kun Yan,Yu-Hang Wang,Yan-Rui Zhao,Jin Zhang,Ya-Hui Wang,Guang-Zhi Zhou,Ji-Xiang Hu
Smart materials whose color and luminescence can be simultaneously tuned by external stimuli are highly desirable for advanced optical and information technologies. Achieving independent yet coupled control over both photochromism and emission, particularly a dual fluorescence-phosphorescence output, remains difficult, often hampered by poor electronic communication between functional units. We address this challenge with a new metal-organic framework, (H3-TPB)2·Zn4(C2O4)6·SO4. Its structure combines an oxalate-zinc photochromic layer as an electron donor with freely incorporated protonated 1,3,5-tris(4-pyridyl)benzene ligands, which act as electron acceptors and emitters. This design enables reversible ligand-to-ligand electron transfer upon light exposure, triggering a fast color change from orange-red to purple-black. Under 270 nm excitation, the material displays tunable dual emission. The fluorescence/phosphorescence intensity ratio and the overall emission color can be reversibly switched between violet and white through photoinduced radical formation and subsequent thermal elimination. These properties are successfully applied to high-resolution ink-free printing and dynamic information encryption. Our work demonstrates a general electron-transfer approach to create multimodal photoactive materials with synchronized and reversible optical responses.
{"title":"Electron-Transfer-Mediated Dynamic Control of Photochromism and Fluorescence/Phosphorescence in a Smart Metal-Organic Framework.","authors":"Qi-Yue Xin,Shuai Liang,Shi-Kun Yan,Yu-Hang Wang,Yan-Rui Zhao,Jin Zhang,Ya-Hui Wang,Guang-Zhi Zhou,Ji-Xiang Hu","doi":"10.1021/acs.inorgchem.6c00080","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00080","url":null,"abstract":"Smart materials whose color and luminescence can be simultaneously tuned by external stimuli are highly desirable for advanced optical and information technologies. Achieving independent yet coupled control over both photochromism and emission, particularly a dual fluorescence-phosphorescence output, remains difficult, often hampered by poor electronic communication between functional units. We address this challenge with a new metal-organic framework, (H3-TPB)2·Zn4(C2O4)6·SO4. Its structure combines an oxalate-zinc photochromic layer as an electron donor with freely incorporated protonated 1,3,5-tris(4-pyridyl)benzene ligands, which act as electron acceptors and emitters. This design enables reversible ligand-to-ligand electron transfer upon light exposure, triggering a fast color change from orange-red to purple-black. Under 270 nm excitation, the material displays tunable dual emission. The fluorescence/phosphorescence intensity ratio and the overall emission color can be reversibly switched between violet and white through photoinduced radical formation and subsequent thermal elimination. These properties are successfully applied to high-resolution ink-free printing and dynamic information encryption. Our work demonstrates a general electron-transfer approach to create multimodal photoactive materials with synchronized and reversible optical responses.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147489866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-20DOI: 10.1021/acs.inorgchem.6c00647
Min Yan,Baoguo Chen,Yunhe You,Liangtian Duan,Taiyao Wang,Xinyu Wang,Yaxin Jiang,Shuyuan Zhao,Shuai Zhang,Guoxun Ji,Dan Li,Yihui Yuan,Ning Wang,Xia Wang
High-energy electron irradiation provides an exceptionally fast, energy-dense route to fabricate porous crystalline frameworks, yet its utility for MOFs is fundamentally limited by a trade-off between accelerated crystallization and radiation-induced damage. Here, we show that this trade-off can be actively navigated by the systematic modulation of the irradiation dose. Using MOF-76 as a model, we identify a dose-dependent maturation regime centered at 120 kGy, at which the material retains high crystallinity while exhibiting a maximized concentration of beneficial defects. Comprehensive characterization confirms the coexistence of preserved framework order and enhanced defect density at this dose. The optimally defective MOF-76 displays markedly improved uranyl ion uptake, reaching a maximum adsorption capacity of 441 mg g-1, which is 4.4-fold higher than that of solvothermally synthesized MOF-76, outperforming both the pristine material and samples produced at other doses in terms of capacity and adsorption kinetics. These results establish dose-controlled electron-beam irradiation as a practical means to tailor defect landscapes in MOFs, enabling the rational design of high-performance adsorbents for radionuclide remediation and related separations.
{"title":"In Situ Synthesis and Defect Engineering of MOF-76 by Electron Beam Irradiation: Balancing Crystallinity and Defects for Uranyl Capture.","authors":"Min Yan,Baoguo Chen,Yunhe You,Liangtian Duan,Taiyao Wang,Xinyu Wang,Yaxin Jiang,Shuyuan Zhao,Shuai Zhang,Guoxun Ji,Dan Li,Yihui Yuan,Ning Wang,Xia Wang","doi":"10.1021/acs.inorgchem.6c00647","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00647","url":null,"abstract":"High-energy electron irradiation provides an exceptionally fast, energy-dense route to fabricate porous crystalline frameworks, yet its utility for MOFs is fundamentally limited by a trade-off between accelerated crystallization and radiation-induced damage. Here, we show that this trade-off can be actively navigated by the systematic modulation of the irradiation dose. Using MOF-76 as a model, we identify a dose-dependent maturation regime centered at 120 kGy, at which the material retains high crystallinity while exhibiting a maximized concentration of beneficial defects. Comprehensive characterization confirms the coexistence of preserved framework order and enhanced defect density at this dose. The optimally defective MOF-76 displays markedly improved uranyl ion uptake, reaching a maximum adsorption capacity of 441 mg g-1, which is 4.4-fold higher than that of solvothermally synthesized MOF-76, outperforming both the pristine material and samples produced at other doses in terms of capacity and adsorption kinetics. These results establish dose-controlled electron-beam irradiation as a practical means to tailor defect landscapes in MOFs, enabling the rational design of high-performance adsorbents for radionuclide remediation and related separations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147483673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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