Pub Date : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05176
Shuai Tang,Zhehong Liu,Alexey V. Ushakov,Fedor Temnikov,Xubin Ye,Zhao Pan,Chien-Te Chen,Chang-Yang Kuo,Zhiwei Hu,Sergey V. Streltsov,Youwen Long
An A- and B-site-ordered quadruple perovskite oxide LaCu3Ni2Re2O12 was synthesized at 9 GPa and 1323 K. The crystal structure adopts a cubic space group of Pn-3 with the lattice constant a = 7.4961(1) Å. Bond valence sum calculation and X-ray absorption spectroscopy suggest the charge distribution to be La3+Cu2+3Ni2+2Re5.5+2O12. A ferrimagnetic transition arising from the Cu2+(↑)-Ni2+(↑)-Re5.5+(↓) spin coupling is found to occur at a Curie temperature of TC ≈ 210 K. First-principles calculations suggest a half-metallic electronic band structure for LaCu3Ni2Re2O12 with an energy gap of about 1.9 eV at the up-spin channel and a conducting band at the down-spin channel. By comparison with other isostructural LaCu3B2Re2O12 (B = Fe, Co, Ni) perovskites, we find that the electronic configuration of Re dominates the Curie temperature, as well as the half-metallic band gap.
{"title":"B-Site-Tuned Curie Temperature and Band Gap in Half-Metallic LaCu3B2Re2O12 (B = Fe, Co, Ni) Quadruple Perovskite Oxides","authors":"Shuai Tang,Zhehong Liu,Alexey V. Ushakov,Fedor Temnikov,Xubin Ye,Zhao Pan,Chien-Te Chen,Chang-Yang Kuo,Zhiwei Hu,Sergey V. Streltsov,Youwen Long","doi":"10.1021/acs.inorgchem.5c05176","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05176","url":null,"abstract":"An A- and B-site-ordered quadruple perovskite oxide LaCu3Ni2Re2O12 was synthesized at 9 GPa and 1323 K. The crystal structure adopts a cubic space group of Pn-3 with the lattice constant a = 7.4961(1) Å. Bond valence sum calculation and X-ray absorption spectroscopy suggest the charge distribution to be La3+Cu2+3Ni2+2Re5.5+2O12. A ferrimagnetic transition arising from the Cu2+(↑)-Ni2+(↑)-Re5.5+(↓) spin coupling is found to occur at a Curie temperature of TC ≈ 210 K. First-principles calculations suggest a half-metallic electronic band structure for LaCu3Ni2Re2O12 with an energy gap of about 1.9 eV at the up-spin channel and a conducting band at the down-spin channel. By comparison with other isostructural LaCu3B2Re2O12 (B = Fe, Co, Ni) perovskites, we find that the electronic configuration of Re dominates the Curie temperature, as well as the half-metallic band gap.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"21 4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111241","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 : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05578
Felix Kracht, Jitpisut Poolwong, Natascha M. Roth, Yucang Liang, Cäcilia Maichle-Mössmer, Reiner Anwander
Recent advances have shown that light metal pyrazolate complexes not only achieve high CO2 uptake but are also able to convert epoxides and CO2 to cyclic carbonates catalytically. Surface organometallic chemistry (SOMC) combines reactive metal complexes with the durability and robustness of a support material to form environmentally even more benign materials for CO2 capture and conversion. In this study, light metal pyrazolates with a variety of oxidation states and ionic radii were grafted onto mesoporous silica SBA-15500 affording the hybrid materials [Mg(pztBu2)2]2@SBA-15500, Al(pztBu2)3@SBA-15500, Ti+IV(pzMe2)4@SBA-15500, and Ti+III(pztBu2)3@SBA-15500. The hybrid materials were characterized via N2 physisorption, elemental analysis, ICP/OES, DRIFTS, and solid-state NMR spectroscopy, suggesting successful grafting with monometallic surface species and revealing a CO2 uptake of up to 11 wt%. In addition, Ti+IV(pzMe2)[OSi(OtBu)3]3 was synthesized as a model complex for surface species likely present for Ti+IV(pzMe2)4@SBA-15500. Complex Ti+IV(pzMe2)[OSi(OtBu)3]3 is also able to insert CO2 under the formation of the carbamate complex Ti+IV(CO2·pzMe2)[OSi(OtBu)3]3, emulating material CO2@Ti+IV(pzMe2)4@SBA-15500. All hybrid materials under study are active catalysts in the cycloaddition of epoxides with CO2 to form cyclic carbonates. The magnesium hybrid material [Mg(pztBu2)2]2@SBA-15500 exceeds its homogeneous congener, featuring high conversion even for bulkier epoxides along with a desirable reusability.
{"title":"Light Metal Pyrazolates Grafted onto Periodic Mesoporous Silica for Carbon Dioxide Capture and Transformation","authors":"Felix Kracht, Jitpisut Poolwong, Natascha M. Roth, Yucang Liang, Cäcilia Maichle-Mössmer, Reiner Anwander","doi":"10.1021/acs.inorgchem.5c05578","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05578","url":null,"abstract":"Recent advances have shown that light metal pyrazolate complexes not only achieve high CO<sub>2</sub> uptake but are also able to convert epoxides and CO<sub>2</sub> to cyclic carbonates catalytically. Surface organometallic chemistry (SOMC) combines reactive metal complexes with the durability and robustness of a support material to form environmentally even more benign materials for CO<sub>2</sub> capture and conversion. In this study, light metal pyrazolates with a variety of oxidation states and ionic radii were grafted onto mesoporous silica SBA-15<sub>500</sub> affording the hybrid materials [Mg(pz<sup><i>t</i>Bu2</sup>)<sub>2</sub>]<sub>2</sub>@SBA-15<sub>500</sub>, Al(pz<sup><i>t</i>Bu2</sup>)<sub>3</sub>@SBA-15<sub>500</sub>, Ti<sup>+IV</sup>(pz<sup>Me2</sup>)<sub>4</sub>@SBA-15<sub>500</sub>, and Ti<sup>+III</sup>(pz<sup><i>t</i>Bu2</sup>)<sub>3</sub>@SBA-15<sub>500</sub>. The hybrid materials were characterized via N<sub>2</sub> physisorption, elemental analysis, ICP/OES, DRIFTS, and solid-state NMR spectroscopy, suggesting successful grafting with monometallic surface species and revealing a CO<sub>2</sub> uptake of up to 11 wt%. In addition, Ti<sup>+IV</sup>(pz<sup>Me2</sup>)[OSi(O<i>t</i>Bu)<sub>3</sub>]<sub>3</sub> was synthesized as a model complex for surface species likely present for Ti<sup>+IV</sup>(pz<sup>Me2</sup>)<sub>4</sub>@SBA-15<sub>500</sub>. Complex Ti<sup>+IV</sup>(pz<sup>Me2</sup>)[OSi(O<i>t</i>Bu)<sub>3</sub>]<sub>3</sub> is also able to insert CO<sub>2</sub> under the formation of the carbamate complex Ti<sup>+IV</sup>(CO<sub>2</sub>·pz<sup>Me2</sup>)[OSi(O<i>t</i>Bu)<sub>3</sub>]<sub>3</sub>, emulating material CO<sub>2</sub>@Ti<sup>+IV</sup>(pz<sup>Me2</sup>)<sub>4</sub>@SBA-15<sub>500</sub>. All hybrid materials under study are active catalysts in the cycloaddition of epoxides with CO<sub>2</sub> to form cyclic carbonates. The magnesium hybrid material [Mg(pz<sup><i>t</i>Bu2</sup>)<sub>2</sub>]<sub>2</sub>@SBA-15<sub>500</sub> exceeds its homogeneous congener, featuring high conversion even for bulkier epoxides along with a desirable reusability.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101947","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 : 2026-02-03DOI: 10.1021/acs.inorgchem.5c04977
Fenglin Wang, Manlan Guo, Xianjie Yang, Youpeng Li, Jingbo Liu, Hao Wan, Gen Chen, Ning Zhang, Xiaohe Liu, Renzhi Ma
The chemical exfoliation of layered metal hydroxides (LMHs) is a cutting-edge technology to obtain unilaminar and few-layer LMH nanosheets with positive charges and an ultrathin thickness, which widely serve as building blocks for functional composites in emerging fields. However, the preparation of high-quality monolayers with a large lateral dimension and regular morphology and the investigation of the exfoliation mechanism remain formidable challenges. Herein, uniform hexagonal NiCo LMH nanosheets were prepared by directly delaminating the well-crystallized α-type NiCo LMH nanoplate precursor in formamide with the assistance of mild heating. A plausible exfoliation mechanism suggests that formamide diffuses rapidly with the assistance of heating, facilitating expansion of the interlayer spacing of the LMH bulk. Subsequently, the precursor undergoes a gradual delamination process to form uniform hexagonal monolayers, as the interlayer force diminishes. Moreover, the positively charged LMH nanosheets are utilized as nanoblocks to electrostatically adsorb anionic polystyrene sodium 4-sulfonate (PSS) or negatively charged reduced graphene oxide (rGO) via a layer-by-layer (LBL) self-assembly method. The constructed (NiCo LMH/PSS)n and (rGO/NiCo LMH)n multilayer heterostructure films are highly viable in electrochemical applications.
{"title":"Unraveling the Tailored Exfoliation Mechanism and Electrochemical Behavior of α-NiCo Hydroxide Nanoplates for Water-Splitting Catalysis","authors":"Fenglin Wang, Manlan Guo, Xianjie Yang, Youpeng Li, Jingbo Liu, Hao Wan, Gen Chen, Ning Zhang, Xiaohe Liu, Renzhi Ma","doi":"10.1021/acs.inorgchem.5c04977","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04977","url":null,"abstract":"The chemical exfoliation of layered metal hydroxides (LMHs) is a cutting-edge technology to obtain unilaminar and few-layer LMH nanosheets with positive charges and an ultrathin thickness, which widely serve as building blocks for functional composites in emerging fields. However, the preparation of high-quality monolayers with a large lateral dimension and regular morphology and the investigation of the exfoliation mechanism remain formidable challenges. Herein, uniform hexagonal NiCo LMH nanosheets were prepared by directly delaminating the well-crystallized α-type NiCo LMH nanoplate precursor in formamide with the assistance of mild heating. A plausible exfoliation mechanism suggests that formamide diffuses rapidly with the assistance of heating, facilitating expansion of the interlayer spacing of the LMH bulk. Subsequently, the precursor undergoes a gradual delamination process to form uniform hexagonal monolayers, as the interlayer force diminishes. Moreover, the positively charged LMH nanosheets are utilized as nanoblocks to electrostatically adsorb anionic polystyrene sodium 4-sulfonate (PSS) or negatively charged reduced graphene oxide (rGO) via a layer-by-layer (LBL) self-assembly method. The constructed (NiCo LMH/PSS)<sub><i>n</i></sub> and (rGO/NiCo LMH)<sub><i>n</i></sub> multilayer heterostructure films are highly viable in electrochemical applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"87 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101924","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 design and synthesis of outstanding nonlinear optical (NLO) crystals continue to represent a pivotal challenge in advanced laser technologies. Herein, two new zero-dimensional (0D) organic–inorganic hybrid antimony halides, C4H9N5SbX5·H2O (X = Cl, Br) featuring [SbX5] square pyramids, were successfully synthesized by three-in-one integrating a Sb3+ ion with a stereochemically active lone pair (SCALP), π-conjugated organic (C4H9N5)2+ cation, and halide anion. They adopt trigonal noncentrosymmetric (NCS) space groups P32 and P31, respectively. Both exhibit outstanding comprehensive NLO properties, featuring phase-matchable second-harmonic generation (SHG) intensities around 3.8 and 3.9 times that of KDP, respectively, broad optical bandgaps of 3.17 and 2.68 eV, and adequate birefringence of 0.12 and 0.10 at 546 nm, demonstrating their significant potential as nonlinear optical materials. Theoretical studies and structural analyses reveal that their excellent optical properties originate from the synergistic effect of organic cations and inorganic [SbX5] square pyramids. This work establishes a rational design framework for guiding the development of advanced NLO crystals.
{"title":"Unlocking Strong SHG Response and Large Birefringence in Hybrid Antimony Halides via a Three-in-One Strategy","authors":"Yu-Qi Xu,Yi-Fan Fu,Wen-Dong Yao,Yu-Mei Zhang,Liming Kong,Wenlong Liu,Jiajing Wu","doi":"10.1021/acs.inorgchem.5c06108","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c06108","url":null,"abstract":"The design and synthesis of outstanding nonlinear optical (NLO) crystals continue to represent a pivotal challenge in advanced laser technologies. Herein, two new zero-dimensional (0D) organic–inorganic hybrid antimony halides, C4H9N5SbX5·H2O (X = Cl, Br) featuring [SbX5] square pyramids, were successfully synthesized by three-in-one integrating a Sb3+ ion with a stereochemically active lone pair (SCALP), π-conjugated organic (C4H9N5)2+ cation, and halide anion. They adopt trigonal noncentrosymmetric (NCS) space groups P32 and P31, respectively. Both exhibit outstanding comprehensive NLO properties, featuring phase-matchable second-harmonic generation (SHG) intensities around 3.8 and 3.9 times that of KDP, respectively, broad optical bandgaps of 3.17 and 2.68 eV, and adequate birefringence of 0.12 and 0.10 at 546 nm, demonstrating their significant potential as nonlinear optical materials. Theoretical studies and structural analyses reveal that their excellent optical properties originate from the synergistic effect of organic cations and inorganic [SbX5] square pyramids. This work establishes a rational design framework for guiding the development of advanced NLO crystals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"253 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111239","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 : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05167
Colin Lawler, Yu Zhang
Treatment of Ti(NMe2)4 with diphenylphosphinic amides Ph2P(O)(NHR) (R = Me, Ph) followed by reaction with tert-butylamine afforded dimeric complexes {Ti(NtBu)[κ2-Ph2P(O)(NR)][μ2-Ph2P(O)(NR)]}2 (R = Ph, 3; Me, 4), which were characterized crystallographically. Variable-temperature NMR studies demonstrated significant structural flexibility of both compounds in solution, and Eyring analysis suggests intramolecular conformational fluxionality of the eight-membered Ti2N2P2O2 metallacycles. While nonemissive in THF solution at room temperature, both complexes exhibit aggregation-induced emission upon the addition of hexane as a counter solvent. Solid-state photoluminescence bands occur with maxima at 648 and 632 nm for 3 and 4, respectively, with quantum yields of 4.3% and 6.3% and long-lived emission lifetimes (6.8 and 3.4 μs, respectively). Time-dependent density functional theory calculations reveal that the low-energy absorption features originate from mixed π(Ti=N) to π(P-phenyl) and π(Ti=N) to d(Ti) charge transfer transitions.
{"title":"Aggregation-Induced Emission from Titanium Complexes Supported by Imido and Phosphinic Amidato Ligands","authors":"Colin Lawler, Yu Zhang","doi":"10.1021/acs.inorgchem.5c05167","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05167","url":null,"abstract":"Treatment of Ti(NMe<sub>2</sub>)<sub>4</sub> with diphenylphosphinic amides Ph<sub>2</sub>P(O)(NHR) (R = Me, Ph) followed by reaction with <i>tert</i>-butylamine afforded dimeric complexes {Ti(N<sup><i>t</i></sup>Bu)[κ<sup>2</sup>-Ph<sub>2</sub>P(O)(NR)][μ<sub>2</sub>-Ph<sub>2</sub>P(O)(NR)]}<sub>2</sub> (R = Ph, <b>3</b>; Me, <b>4</b>), which were characterized crystallographically. Variable-temperature NMR studies demonstrated significant structural flexibility of both compounds in solution, and Eyring analysis suggests intramolecular conformational fluxionality of the eight-membered Ti<sub>2</sub>N<sub>2</sub>P<sub>2</sub>O<sub>2</sub> metallacycles. While nonemissive in THF solution at room temperature, both complexes exhibit aggregation-induced emission upon the addition of hexane as a counter solvent. Solid-state photoluminescence bands occur with maxima at 648 and 632 nm for <b>3</b> and <b>4</b>, respectively, with quantum yields of 4.3% and 6.3% and long-lived emission lifetimes (6.8 and 3.4 μs, respectively). Time-dependent density functional theory calculations reveal that the low-energy absorption features originate from mixed π<sub>(Ti=N)</sub> to π<sub>(P-phenyl)</sub> and π<sub>(Ti=N)</sub> to d<sub>(Ti)</sub> charge transfer transitions.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"92 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101944","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 : 2026-02-03DOI: 10.1021/acs.inorgchem.5c05011
Yuting Chen,Weicheng Tang,Xiaoyu Guo,Xiaohan Zhao,Yunmei Du,Jun Xing,Lei Wang,Kang Liu
In the pursuit of a technological breakthrough in zinc-air batteries, it is critical to find economical, durable, and high-performance catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) to accelerate the slow reaction kinetics. Herein, a one-pot method was employed to synthesize the polymer within a mixed solvent of CHCl3 and CH3OH (v/v = 2:1). The resulting polymer can be well-dispersed in deionized water to form an aqueous metal–organic gel (MOG). Testing has revealed that Co-MOG exhibits dual catalytic properties for both the OER and ORR, a characteristic that is notably rare in original MOG materials. Furthermore, it demonstrates exceptional long-term charge–discharge cycling stability in zinc-air batteries, outperforming several reported Co-based catalysts for the OER and ORR. X-ray absorption spectroscopy and density-functional theory (DFT) calculations indicate that the CoN3 configuration serves as the catalytically active site of the material. In conclusion, this work supports the application of MOGs as unique bifunctional electrocatalysts for the OER and ORR in metal-air batteries.
{"title":"Hydrated Tripodal Polydentate Terpyridine Cobalt Complex-Based Metal–Organic Gel as a Bifunctional OER/ORR Electrocatalyst","authors":"Yuting Chen,Weicheng Tang,Xiaoyu Guo,Xiaohan Zhao,Yunmei Du,Jun Xing,Lei Wang,Kang Liu","doi":"10.1021/acs.inorgchem.5c05011","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05011","url":null,"abstract":"In the pursuit of a technological breakthrough in zinc-air batteries, it is critical to find economical, durable, and high-performance catalysts for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) to accelerate the slow reaction kinetics. Herein, a one-pot method was employed to synthesize the polymer within a mixed solvent of CHCl3 and CH3OH (v/v = 2:1). The resulting polymer can be well-dispersed in deionized water to form an aqueous metal–organic gel (MOG). Testing has revealed that Co-MOG exhibits dual catalytic properties for both the OER and ORR, a characteristic that is notably rare in original MOG materials. Furthermore, it demonstrates exceptional long-term charge–discharge cycling stability in zinc-air batteries, outperforming several reported Co-based catalysts for the OER and ORR. X-ray absorption spectroscopy and density-functional theory (DFT) calculations indicate that the CoN3 configuration serves as the catalytically active site of the material. In conclusion, this work supports the application of MOGs as unique bifunctional electrocatalysts for the OER and ORR in metal-air batteries.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111243","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 : 2026-02-02DOI: 10.1021/acs.inorgchem.5c05814
Isabel Huck,Niels Kubitza,Tom Keil,Marius Schlapp,Robert Winkler,Prajna Bhatt,Christoph Schlueter,Pardeep K. Thakur,Tien-Lin Lee,Paweł P. Michałowski,Leopoldo Molina-Luna,Anna Regoutz,Christina S. Birkel
MAX phases are an extremely versatile family of layered compounds that usually consist of an early to-mid transition metal (M-element), a main group element (mainly groups 13–15) or late transition metal (A-element) and carbon and/or nitrogen (X-element). It is therefore not too surprising that in addition to the roughly 70 compounds with 211 stoichiometry, there exist many solid solutions with mixed elements on the M- and A-site, respectively. Much less common are solid solution phases with mixed elements on both M- and A-site simultaneously (double-site solid solutions), as well as solid solutions on the X-site (carbonitride MAX phases). Challenging these restrictions in the chemical composition space, we present here for the first time (V0.2Cr0.8)2(Ga0.5Ge0.5)(C0.6N0.4) as a new carbonitride member of the MAX phase family, containing solid solutions on all three lattice sites simultaneously. This triple-site solid solution MAX phase is synthesized by high-temperature solid-state methods, and we demonstrate that it is possible to use two different nitrogen-containing precursors (VN and Cr2N), respectively. Structure, morphology and chemical composition are characterized by X-ray powder diffraction (XRD), electron microscopy (SEM/TEM), secondary ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (HAXPES).
{"title":"Synthesis of (V0.2Cr0.8)2(Ga0.5Ge0.5)(C0.6N0.4), a Triple-Site Solid Solution MAX Phase","authors":"Isabel Huck,Niels Kubitza,Tom Keil,Marius Schlapp,Robert Winkler,Prajna Bhatt,Christoph Schlueter,Pardeep K. Thakur,Tien-Lin Lee,Paweł P. Michałowski,Leopoldo Molina-Luna,Anna Regoutz,Christina S. Birkel","doi":"10.1021/acs.inorgchem.5c05814","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05814","url":null,"abstract":"MAX phases are an extremely versatile family of layered compounds that usually consist of an early to-mid transition metal (M-element), a main group element (mainly groups 13–15) or late transition metal (A-element) and carbon and/or nitrogen (X-element). It is therefore not too surprising that in addition to the roughly 70 compounds with 211 stoichiometry, there exist many solid solutions with mixed elements on the M- and A-site, respectively. Much less common are solid solution phases with mixed elements on both M- and A-site simultaneously (double-site solid solutions), as well as solid solutions on the X-site (carbonitride MAX phases). Challenging these restrictions in the chemical composition space, we present here for the first time (V0.2Cr0.8)2(Ga0.5Ge0.5)(C0.6N0.4) as a new carbonitride member of the MAX phase family, containing solid solutions on all three lattice sites simultaneously. This triple-site solid solution MAX phase is synthesized by high-temperature solid-state methods, and we demonstrate that it is possible to use two different nitrogen-containing precursors (VN and Cr2N), respectively. Structure, morphology and chemical composition are characterized by X-ray powder diffraction (XRD), electron microscopy (SEM/TEM), secondary ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (HAXPES).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"79 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097832","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 : 2026-02-02DOI: 10.1021/acs.inorgchem.5c05826
Ye Tao,Xiaohui Zhang,Chenglong Xu,Qianshuang Lu,Jiarui Tan,Yingjie Li,Junzi Li,Jianke Pan,Feng Su,Tingchao He,Haifeng Dong,Heng Wang,Zhi Chen,Chengmin Ji,Xiujun Yu,Xiaopeng Li
The development of high-performance deep-ultraviolet (deep-UV) second-order nonlinear optical (NLO) crystals that simultaneously combine noncentrosymmetric crystal structure, broad transparency, strong second-harmonic generation (SHG) activity, and high thermal and chemical stability remains a formidable challenge due to intrinsic trade-offs among these properties. Herein, we present a multicomponent structural design strategy that enables the rational synthesis of a new KBe2BO3F2 (KBBF)-like rubidium lanthanum sulfate, RbLa(SO4)2. In this crystal, the highly polarizable [LaO10] unit substitutes for [BeO3F] to enhance polarization, the non-π-conjugated [SO4] group replaces [BO3] to maximize the SHG response, and the alkali metal Rb+ cation improves optical transparency and structural robustness. Consequently, RbLa(SO4)2 exhibits excellent deep-UV transparency, featuring an absorption cutoff below 190 nm, along with pronounced SHG responses about 120 times that of Y-cut quartz at 880 nm and 1.5 times stronger than that of KH2PO4 at 1064 nm. Moreover, the crystal shows exceptional thermal stability, maintaining structural integrity up to 1000 °C, making it among the most thermally robust NLO sulfates reported to date. Experimental and theoretical analyses reveal that the synergistic alignment of polarizable [LaO10] polyhedra and [SO4] tetrahedra underpins their high NLO performance. This study provides a promising design paradigm for rare earth sulfate-based deep-UV NLO crystals.
{"title":"RbLa(SO4)2: A KBBF-like Deep-UV Transparent Rare Earth Sulfate with Strong SHG Response and High Thermal Stability Enabled by Multicomponent Structural Design","authors":"Ye Tao,Xiaohui Zhang,Chenglong Xu,Qianshuang Lu,Jiarui Tan,Yingjie Li,Junzi Li,Jianke Pan,Feng Su,Tingchao He,Haifeng Dong,Heng Wang,Zhi Chen,Chengmin Ji,Xiujun Yu,Xiaopeng Li","doi":"10.1021/acs.inorgchem.5c05826","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05826","url":null,"abstract":"The development of high-performance deep-ultraviolet (deep-UV) second-order nonlinear optical (NLO) crystals that simultaneously combine noncentrosymmetric crystal structure, broad transparency, strong second-harmonic generation (SHG) activity, and high thermal and chemical stability remains a formidable challenge due to intrinsic trade-offs among these properties. Herein, we present a multicomponent structural design strategy that enables the rational synthesis of a new KBe2BO3F2 (KBBF)-like rubidium lanthanum sulfate, RbLa(SO4)2. In this crystal, the highly polarizable [LaO10] unit substitutes for [BeO3F] to enhance polarization, the non-π-conjugated [SO4] group replaces [BO3] to maximize the SHG response, and the alkali metal Rb+ cation improves optical transparency and structural robustness. Consequently, RbLa(SO4)2 exhibits excellent deep-UV transparency, featuring an absorption cutoff below 190 nm, along with pronounced SHG responses about 120 times that of Y-cut quartz at 880 nm and 1.5 times stronger than that of KH2PO4 at 1064 nm. Moreover, the crystal shows exceptional thermal stability, maintaining structural integrity up to 1000 °C, making it among the most thermally robust NLO sulfates reported to date. Experimental and theoretical analyses reveal that the synergistic alignment of polarizable [LaO10] polyhedra and [SO4] tetrahedra underpins their high NLO performance. This study provides a promising design paradigm for rare earth sulfate-based deep-UV NLO crystals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098049","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}
As a broad-spectrum antimicrobial agent, furaltadone is widely used in various sterilization fields. They are easily excreted into wastewater, resulting in bioaccumulation and posing risks to the local environment. In this work, a new metal–organic framework (MOF) with a previously unreported self-catenated net feature was synthesized using an asymmetric linker to remove the furaltadone antibiotic from aqueous media. The distinctive ring arrangement within the network is guided by the highly unsymmetrical organic linker, while strong hydrogen bonds between neighboring building units provide additional stabilization to this structure. Boasting high surface area and large pore volume, the MOF with self-entanglement strongly interacts with furaltadone molecules via prominent interaction sites. Highly efficient removal of furaltadone under neutral conditions with rapid uptake, high capacity (95.1% adsorption rate and up to 278.6 mg g–1 maximum monolayer capacity) and cyclability was achieved. These attributes establish the presented MOF as a promising adsorbent for mitigating antibiotic contamination in environmental remediation.
{"title":"A Self-Catenated Metal–Organic Framework with Asymmetric Linkers and Its Adsorption of Furaltadone Antibiotic","authors":"Xin-Yuan Wu,Yuqian Sun,Jian-Mei Lu,Qiaowei Li,Li-Xiong Shao","doi":"10.1021/acs.inorgchem.5c05559","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05559","url":null,"abstract":"As a broad-spectrum antimicrobial agent, furaltadone is widely used in various sterilization fields. They are easily excreted into wastewater, resulting in bioaccumulation and posing risks to the local environment. In this work, a new metal–organic framework (MOF) with a previously unreported self-catenated net feature was synthesized using an asymmetric linker to remove the furaltadone antibiotic from aqueous media. The distinctive ring arrangement within the network is guided by the highly unsymmetrical organic linker, while strong hydrogen bonds between neighboring building units provide additional stabilization to this structure. Boasting high surface area and large pore volume, the MOF with self-entanglement strongly interacts with furaltadone molecules via prominent interaction sites. Highly efficient removal of furaltadone under neutral conditions with rapid uptake, high capacity (95.1% adsorption rate and up to 278.6 mg g–1 maximum monolayer capacity) and cyclability was achieved. These attributes establish the presented MOF as a promising adsorbent for mitigating antibiotic contamination in environmental remediation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098051","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 : 2026-02-02DOI: 10.1021/acs.inorgchem.5c05866
Yibo Cui, Jiawei Lin, Lei Gao, Yuhe Shao, Ruonan Yao, Zhongnan Guo, Jing Zhao, Quanlin Liu
Ten new hybrid halides were synthesized using three pyridine-based organic cations with progressively increasing side chain lengths, including 2-(methylamino)pyridine (MAP), 2-[(methylamino)methyl]pyridine (MAMP), and 2-(2-methylaminoethyl)pyridine (MAEP). Systematic variation of the chain length, halide (Cl, Br, I), and metal center (Sb, Bi) enables controlled tuning of crystal symmetry, intermolecular interactions, local distortions, and optical behavior. The medium-length, doubly protonated MAMP cation guides orientational distortions along one-dimensional inorganic chains, stabilizing six noncentrosymmetric P212121 phases exhibiting strong second-harmonic generation (up to ∼1.2× KDP). Halide substitution effectively narrows the band gap and tailors absorption and emission behavior, while all compounds display ns2-type broadband luminescence at 80 K. Thermal analysis confirms high stability (280–330 °C). Notably, (MAP)2SbBr5 exhibits a distinct melting event near 153 °C with an average entropy change of 108.12 J·mol–1·K–1. Density functional theory shows inorganic-dominated valence-band maximum (VBM) and organic-dominated conduction-band minimum (CBM) contributions, demonstrating strong coupling between the structure and electronic properties. This work establishes a structure-guided pathway for rationally designing multifunctional hybrid halides.
{"title":"Structural Tuning via Chain Length for Emergent Second Harmonic Generation in Hybrid Metal Halides","authors":"Yibo Cui, Jiawei Lin, Lei Gao, Yuhe Shao, Ruonan Yao, Zhongnan Guo, Jing Zhao, Quanlin Liu","doi":"10.1021/acs.inorgchem.5c05866","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05866","url":null,"abstract":"Ten new hybrid halides were synthesized using three pyridine-based organic cations with progressively increasing side chain lengths, including 2-(methylamino)pyridine (MAP), 2-[(methylamino)methyl]pyridine (MAMP), and 2-(2-methylaminoethyl)pyridine (MAEP). Systematic variation of the chain length, halide (Cl, Br, I), and metal center (Sb, Bi) enables controlled tuning of crystal symmetry, intermolecular interactions, local distortions, and optical behavior. The medium-length, doubly protonated MAMP cation guides orientational distortions along one-dimensional inorganic chains, stabilizing six noncentrosymmetric <i>P</i>2<sub>1</sub>2<sub>1</sub>2<sub>1</sub> phases exhibiting strong second-harmonic generation (up to ∼1.2× KDP). Halide substitution effectively narrows the band gap and tailors absorption and emission behavior, while all compounds display <i>n</i>s<sup>2</sup>-type broadband luminescence at 80 K. Thermal analysis confirms high stability (280–330 °C). Notably, (MAP)<sub>2</sub>SbBr<sub>5</sub> exhibits a distinct melting event near 153 °C with an average entropy change of 108.12 J·mol<sup>–1</sup>·K<sup>–1</sup>. Density functional theory shows inorganic-dominated valence-band maximum (VBM) and organic-dominated conduction-band minimum (CBM) contributions, demonstrating strong coupling between the structure and electronic properties. This work establishes a structure-guided pathway for rationally designing multifunctional hybrid halides.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101946","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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