Pub Date : 2026-01-29DOI: 10.1021/acs.inorgchem.5c05729
Bao Jiang,Hong-Heng Chen,Lei Wu,Xue-Yin Fu,Maierhaba Abudoureheman,Qun Jing,Yu-Hong Su,Zhao-Hui Chen
Aliovalent substitution involving cations with lone pair electrons is a powerful strategy for designing novel optical materials with enhanced properties. Herein, by substituting Sn4+ with stereochemically active Sn2+ in the α/β-LiSn2(PO4)3 parent structure, we successfully synthesized α/β-Li2SnP2O7 pyrophosphates, achieving a remarkable 5.5 time enhancement in birefringence. This oxidation-state-driven transformation converts the symmetric [SnO6] octahedra in α/β-LiSn2(PO4)3 into highly distorted [SnO4] tetrahedra in α/β-Li2SnP2O7. This conversion leads to the bond length distortion index boosting (from 9.42/9.95 × 10-3 to 47.17/49.21 × 10-3) and the bond angle varying (from 26.97/29.65 deg2 to 1054.2/1122.1 deg2), which triggers the [SnP6O24] clusters into [SnP2O9] three-membered rings, repectively. The increased distortion of Sn-O groups and the decreased symmetry of Sn-P-O blocks enhance the optical anisotropy of the compounds effectively. This aliovalent substitution strategy offers a valuable gudience for amplifying the intrinsically low birefringence of phosphates.
{"title":"Sn4+/Sn2+ Aliovalent Substitution: A Strategy for Local Structure Engineering to Enhance Birefringence and Trigger Structural Symmetry Transition.","authors":"Bao Jiang,Hong-Heng Chen,Lei Wu,Xue-Yin Fu,Maierhaba Abudoureheman,Qun Jing,Yu-Hong Su,Zhao-Hui Chen","doi":"10.1021/acs.inorgchem.5c05729","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05729","url":null,"abstract":"Aliovalent substitution involving cations with lone pair electrons is a powerful strategy for designing novel optical materials with enhanced properties. Herein, by substituting Sn4+ with stereochemically active Sn2+ in the α/β-LiSn2(PO4)3 parent structure, we successfully synthesized α/β-Li2SnP2O7 pyrophosphates, achieving a remarkable 5.5 time enhancement in birefringence. This oxidation-state-driven transformation converts the symmetric [SnO6] octahedra in α/β-LiSn2(PO4)3 into highly distorted [SnO4] tetrahedra in α/β-Li2SnP2O7. This conversion leads to the bond length distortion index boosting (from 9.42/9.95 × 10-3 to 47.17/49.21 × 10-3) and the bond angle varying (from 26.97/29.65 deg2 to 1054.2/1122.1 deg2), which triggers the [SnP6O24] clusters into [SnP2O9] three-membered rings, repectively. The increased distortion of Sn-O groups and the decreased symmetry of Sn-P-O blocks enhance the optical anisotropy of the compounds effectively. This aliovalent substitution strategy offers a valuable gudience for amplifying the intrinsically low birefringence of phosphates.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072897","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}
Ensuring efficient noble metal utilization while maintaining rapid electron transport and long-term durability remains a central challenge in the acidic hydrogen evolution reaction (HER). Herein, we report a platinum catalyst supported on Magneli phase Ti4O7, a conductive oxide obtained via the hydrogen reduction of TiO2(B), in which the support plays an active electronic role rather than serving as an inert scaffold. Electrochemical and spectroscopic analyses reveal that the mixed Ti3+/Ti4+ valence states and high electrical conductivity of Ti4O7 enable strong electronic coupling with Pt, leading to reduced charge-transfer resistance and more favorable hydrogen adsorption kinetics. As a result, the optimized 3 wt % Pt/Ti4O7 catalyst achieves an overpotential of 13 mV at 10 mA cm-2 with sustained activity over 100 h in 0.5 M H2SO4. These findings demonstrate that conductive oxide supports can actively regulate interfacial electron transfer and reaction kinetics, offering a viable strategy for low noble metal loading and high-performance HER catalysts.
确保贵金属的有效利用，同时保持快速的电子传递和长期的耐久性仍然是酸性析氢反应（HER）的核心挑战。本文中，我们报道了一种负载在Magneli相Ti4O7上的铂催化剂，这是一种通过氢还原TiO2(B)获得的导电氧化物，在这种催化剂中，载体起着活跃的电子作用，而不是作为惰性支架。电化学和光谱分析表明，Ti4O7的Ti3+/Ti4+混合价态和高导电性使其与Pt具有强的电子耦合，从而降低了电荷转移阻力和更有利的氢吸附动力学。结果表明，优化后的3 wt % Pt/Ti4O7催化剂在10 mA cm-2下的过电位为13 mV，在0.5 M H2SO4中持续活性超过100小时。这些发现表明，导电氧化物载体可以积极调节界面电子转移和反应动力学，为低贵金属负载和高性能HER催化剂提供了可行的策略。
{"title":"Promoted Electrochemical Hydrogen Evolution Kinetics by Anchoring Pt Nanoparticles on a Conductive Ti4O7 Support.","authors":"Zahid Hussain,Sehrish Nawaz,Zohaib Rana,Wenyu Jia,Muhammad Umer Rafique,Amjad Nisar,Yongmei Chen,Guolei Xiang","doi":"10.1021/acs.inorgchem.5c05062","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05062","url":null,"abstract":"Ensuring efficient noble metal utilization while maintaining rapid electron transport and long-term durability remains a central challenge in the acidic hydrogen evolution reaction (HER). Herein, we report a platinum catalyst supported on Magneli phase Ti4O7, a conductive oxide obtained via the hydrogen reduction of TiO2(B), in which the support plays an active electronic role rather than serving as an inert scaffold. Electrochemical and spectroscopic analyses reveal that the mixed Ti3+/Ti4+ valence states and high electrical conductivity of Ti4O7 enable strong electronic coupling with Pt, leading to reduced charge-transfer resistance and more favorable hydrogen adsorption kinetics. As a result, the optimized 3 wt % Pt/Ti4O7 catalyst achieves an overpotential of 13 mV at 10 mA cm-2 with sustained activity over 100 h in 0.5 M H2SO4. These findings demonstrate that conductive oxide supports can actively regulate interfacial electron transfer and reaction kinetics, offering a viable strategy for low noble metal loading and high-performance HER catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"9 5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146073349","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 : 2026-01-28DOI: 10.1021/acs.inorgchem.5c04930
Jianglan Liu,Jia-Yi Chen,Zhiqiang Peng,Lan Liu,Rong-Zhen Liao,Wenguang Wang
We report nitrite-to-NO reduction using Mo(P^S^S)2 (1, where P^S^S = PhP(o-C6H4S-)2), and explore the protonation of the resulting anionic Mo(IV)-NO complex (2) as a potential for further transformations. In the absence of benzenethiol as an external reductant, both the molybdenum center and the phosphine donor in 1 serve as internal oxygen-atom acceptors, resulting in the formation of Mo(VI)-oxo (3), Mo(IV)-NO (2), and phosphoryl-ligated Mo(IV)-NO (4) complexes, all of which are structurally characterized. Notably, the anionic Mo(IV)-NO complex undergoes sulfur protonation, as demonstrated by the isolation of a rare S···H-N hydrogen-bonded intermediate [(NO)Mo(P^S^S)2][HLut] (5), and the protonated complex (P^S^S)Mo(NO)(P^S^SH) (6).
{"title":"Reduction of Nitrite to NO on a Molybdenum-Thiolate Platform and Protonation of the Anionic Nitrosyl Complex.","authors":"Jianglan Liu,Jia-Yi Chen,Zhiqiang Peng,Lan Liu,Rong-Zhen Liao,Wenguang Wang","doi":"10.1021/acs.inorgchem.5c04930","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04930","url":null,"abstract":"We report nitrite-to-NO reduction using Mo(P^S^S)2 (1, where P^S^S = PhP(o-C6H4S-)2), and explore the protonation of the resulting anionic Mo(IV)-NO complex (2) as a potential for further transformations. In the absence of benzenethiol as an external reductant, both the molybdenum center and the phosphine donor in 1 serve as internal oxygen-atom acceptors, resulting in the formation of Mo(VI)-oxo (3), Mo(IV)-NO (2), and phosphoryl-ligated Mo(IV)-NO (4) complexes, all of which are structurally characterized. Notably, the anionic Mo(IV)-NO complex undergoes sulfur protonation, as demonstrated by the isolation of a rare S···H-N hydrogen-bonded intermediate [(NO)Mo(P^S^S)2][HLut] (5), and the protonated complex (P^S^S)Mo(NO)(P^S^SH) (6).","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"142 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056934","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}
Mn(II)/Ni(II)-salts and 2,5-pyridinedicarboxylic acid (PDA)-based individual supramolecular metallogels (i.e., Mn-PDA and Ni-PDA) are achieved by maintaining specific stoichiometric ratios of distinct metal salts and PDA (i.e., 1:1). 2,5-Pyridinedicarboxylic acid acts as a low-molecular-weight organogelator, and N,N'-dimethylformamide (DMF) is used as a gel-immobilized polar aprotic solvent. Mechanical flexibility, morphology, stimuli-responsiveness, and formation strategy of metallogels are explored. Semiconductor p-n junction of both the metallogels Ni-PDA and Mn-PDA with p-type silicon (p-Si) was investigated in this study. Both Ni-PDA/p-Si and Mn-PDA/p-Si photodetectors effectively exhibit superior semiconducting behavior with low ideality factors (η) of 1.4 and 1.8, respectively, under dark conditions and ON/OFF ratios of 8 and 4.2 at a reverse bias voltage of -2 V for Ni-PDA, and Mn-PDA, respectively. Interestingly, the Ni-PDA/p-Si device shows a higher optical responsivity. Electrical performance of Au/Ni-PDA/Au and Au/Mn-PDA/Au strategy-based Schottky diode photodetectors was also explored, and the photosensitivity (%) of these two different Schottky devices is accounted as ∼102 and ∼1100, respectively. Synthesized metallogels are efficiently potent against pathogenic Gram + ve and -ve bacteria. Both of these metallogels show different levels of effectiveness against individual bacterial strains. Thus, the work might be an excellent example of getting bioelectronic-type flexible self-healing materials for future applications.
{"title":"Self-Healing Antibacterial Metallosupramolecular Soft-Networks: Comparative Studies on Mechanical Flexibility and Semiconducting Device Applications.","authors":"Biswajit Dey,Indrajit Pal,Kunal Kumar Saha,Santanu Majumdar,Moumita Parveen,Arijit Das,Suresh Kumar Yatirajula,Narayan Chandra Mandal","doi":"10.1021/acs.inorgchem.5c04109","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c04109","url":null,"abstract":"Mn(II)/Ni(II)-salts and 2,5-pyridinedicarboxylic acid (PDA)-based individual supramolecular metallogels (i.e., Mn-PDA and Ni-PDA) are achieved by maintaining specific stoichiometric ratios of distinct metal salts and PDA (i.e., 1:1). 2,5-Pyridinedicarboxylic acid acts as a low-molecular-weight organogelator, and N,N'-dimethylformamide (DMF) is used as a gel-immobilized polar aprotic solvent. Mechanical flexibility, morphology, stimuli-responsiveness, and formation strategy of metallogels are explored. Semiconductor p-n junction of both the metallogels Ni-PDA and Mn-PDA with p-type silicon (p-Si) was investigated in this study. Both Ni-PDA/p-Si and Mn-PDA/p-Si photodetectors effectively exhibit superior semiconducting behavior with low ideality factors (η) of 1.4 and 1.8, respectively, under dark conditions and ON/OFF ratios of 8 and 4.2 at a reverse bias voltage of -2 V for Ni-PDA, and Mn-PDA, respectively. Interestingly, the Ni-PDA/p-Si device shows a higher optical responsivity. Electrical performance of Au/Ni-PDA/Au and Au/Mn-PDA/Au strategy-based Schottky diode photodetectors was also explored, and the photosensitivity (%) of these two different Schottky devices is accounted as ∼102 and ∼1100, respectively. Synthesized metallogels are efficiently potent against pathogenic Gram + ve and -ve bacteria. Both of these metallogels show different levels of effectiveness against individual bacterial strains. Thus, the work might be an excellent example of getting bioelectronic-type flexible self-healing materials for future applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070087","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 : 2026-01-28DOI: 10.1021/acs.inorgchem.5c05332
Ali Raza Ayub, Salba,Muhammad Zeshan,Karim Youssef Nabat,Javed Iqbal,Hui Li
In this comprehensive investigation, we present an integrated computational and experimental study of a series of metal-doped supramolecular PDI(β-ala)-GMP complexes using Ag(I)/Co(II)/Zn(II) as central metal ions. The supramolecular assemblies were critically analyzed in terms of optoelectronic properties and electronic behaviors. High-order computational studies, such as noncovalent interaction (NCI) and reduced density gradient (RDG) isosurface mapping, electron density difference maps (EDDM), Hirschfeld surface analysis, and frontier molecular orbital (FMO) theory, gave a more in-depth insight into the electronic structure, charge transfer, and the intermolecular interactions. Additionally, stability indices, natural bond order (NBO) analysis, dipole moment measurements, and full optoelectronic property calculations were done to rationalize structure-property relationships. The formation and stability of the metal-doped supramolecular architectures were experimentally validated by the use of spectroscopic (ultraviolet-visible (UV-vis), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR)) and structural (PXRD) methods. It is important to note that Zn2PDI(GMP)2(H2O)4 complex exhibited a better electronic delocalization and strong intermolecular interactions, thereby making it one of the most promising products in the next-generation photonic and optoelectronic applications. This work provides the design principles of engineering supramolecular materials with the desired optoelectronic properties that lie between computational predictions and experimental assembly.
{"title":"The Metal Coordination Effects on the Optoelectronic Properties of Perylene Diimide and Nucleotide Supramolecular Complex (GMP:PDI: Ag(I)/Co(II)/Zn(II)): Computational and Experimental Studies.","authors":"Ali Raza Ayub, Salba,Muhammad Zeshan,Karim Youssef Nabat,Javed Iqbal,Hui Li","doi":"10.1021/acs.inorgchem.5c05332","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05332","url":null,"abstract":"In this comprehensive investigation, we present an integrated computational and experimental study of a series of metal-doped supramolecular PDI(β-ala)-GMP complexes using Ag(I)/Co(II)/Zn(II) as central metal ions. The supramolecular assemblies were critically analyzed in terms of optoelectronic properties and electronic behaviors. High-order computational studies, such as noncovalent interaction (NCI) and reduced density gradient (RDG) isosurface mapping, electron density difference maps (EDDM), Hirschfeld surface analysis, and frontier molecular orbital (FMO) theory, gave a more in-depth insight into the electronic structure, charge transfer, and the intermolecular interactions. Additionally, stability indices, natural bond order (NBO) analysis, dipole moment measurements, and full optoelectronic property calculations were done to rationalize structure-property relationships. The formation and stability of the metal-doped supramolecular architectures were experimentally validated by the use of spectroscopic (ultraviolet-visible (UV-vis), Fourier transform infrared (FTIR), and nuclear magnetic resonance (NMR)) and structural (PXRD) methods. It is important to note that Zn2PDI(GMP)2(H2O)4 complex exhibited a better electronic delocalization and strong intermolecular interactions, thereby making it one of the most promising products in the next-generation photonic and optoelectronic applications. This work provides the design principles of engineering supramolecular materials with the desired optoelectronic properties that lie between computational predictions and experimental assembly.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070029","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 : 2026-01-28DOI: 10.1021/acs.inorgchem.5c05791
Jie Dong,Man Yu,Xiang Xiong,Xin-Yu Tian,Ning Wang,Xin-Shuo Wang,Yao Xie,Sheng-Li Hou,Bin Zhao
Although the detection of biomarkers epinephrine (EP) and homovanillic acid (HO) is critical for early diagnosis and personalized medicine, the development of a luminescent sensor for their precise quantification remains an ongoing challenge. In this work, a unique porous Hf6-based metal-organic framework (MOF), [Hf6(μ3-O)4(μ3-OH)4(OH)4(H2O)4(PPTA)2]·xS (denoted as 1), with high acid stability was synthesized. It serves as a dual-function luminescence sensor for EP and HO detection, achieving low limits of detection of 9.3 × 10-9 and 1.8 × 10-7 mol/L, respectively. Besides, the thin film 1@CRG can be simply synthesized for visual detection of EP and HO, demonstrating great potential for home-testing use. This work presents a new MOF-based sensing platform, paving the way for advanced multianalyte biomarker detection in clinical diagnostics.
{"title":"An Acid-Resistant Hf6-MOF for the Luminescence Sensing of Biomarkers with High Sensitivity and Selectivity.","authors":"Jie Dong,Man Yu,Xiang Xiong,Xin-Yu Tian,Ning Wang,Xin-Shuo Wang,Yao Xie,Sheng-Li Hou,Bin Zhao","doi":"10.1021/acs.inorgchem.5c05791","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05791","url":null,"abstract":"Although the detection of biomarkers epinephrine (EP) and homovanillic acid (HO) is critical for early diagnosis and personalized medicine, the development of a luminescent sensor for their precise quantification remains an ongoing challenge. In this work, a unique porous Hf6-based metal-organic framework (MOF), [Hf6(μ3-O)4(μ3-OH)4(OH)4(H2O)4(PPTA)2]·xS (denoted as 1), with high acid stability was synthesized. It serves as a dual-function luminescence sensor for EP and HO detection, achieving low limits of detection of 9.3 × 10-9 and 1.8 × 10-7 mol/L, respectively. Besides, the thin film 1@CRG can be simply synthesized for visual detection of EP and HO, demonstrating great potential for home-testing use. This work presents a new MOF-based sensing platform, paving the way for advanced multianalyte biomarker detection in clinical diagnostics.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146069816","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 development of fast and sensitive fluorescence sensors for nitro-explosive detection in aqueous environments remains a critical challenge for security and environmental monitoring. This work presents two novel metal-organic frameworks (MOFs) constructed from tetrakistetrazole-functionalized tetraphenylethylene (H4tazope), an aggregation-induced emission (AIE)-active ligand. Assembled with Cd(II) and Co(II) ions, the multidentate molecule based on the TPE core can afford neutral and anionic coordination polymers 1 and 2 with rare nona- and octa-coordinating bridging modes for each tetrakistetrazole ligand, in which the framework structures show the unprecedented 2D 3-nodal with the point symbol of {32.46.3.42.3.52.4.62.52.42}{3}{46.32.52} and 2-fold interpenetrated (4,12)-connected topological networks, respectively. Detailed research on the use of the luminescent MOF with TPE chromophore attached with four tetrazolyl substituents for highly selective fluorescence-based aqueous-phase explosive detection was also conducted. An unprecedented 2D 3-nodal topological network with AIE-active tetrazolyl-tetraphenylethene ligand exhibits promising application prospects in nitro-explosive detection.
{"title":"AIE-Active Tetrazolyl Tetraphenylethylene-Based Metal-Organic Framework as Highly Selective Chemosensor for Nitro Explosives.","authors":"Senyu Zhang,Haoyu Chen,Chenxi Xu,Jinxia Ren,Yonghua Li,Kang Xiao,Jian Su,Shi Wang,Kenneth Yin Zhang","doi":"10.1021/acs.inorgchem.5c05084","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05084","url":null,"abstract":"The development of fast and sensitive fluorescence sensors for nitro-explosive detection in aqueous environments remains a critical challenge for security and environmental monitoring. This work presents two novel metal-organic frameworks (MOFs) constructed from tetrakistetrazole-functionalized tetraphenylethylene (H4tazope), an aggregation-induced emission (AIE)-active ligand. Assembled with Cd(II) and Co(II) ions, the multidentate molecule based on the TPE core can afford neutral and anionic coordination polymers 1 and 2 with rare nona- and octa-coordinating bridging modes for each tetrakistetrazole ligand, in which the framework structures show the unprecedented 2D 3-nodal with the point symbol of {32.46.3.42.3.52.4.62.52.42}{3}{46.32.52} and 2-fold interpenetrated (4,12)-connected topological networks, respectively. Detailed research on the use of the luminescent MOF with TPE chromophore attached with four tetrazolyl substituents for highly selective fluorescence-based aqueous-phase explosive detection was also conducted. An unprecedented 2D 3-nodal topological network with AIE-active tetrazolyl-tetraphenylethene ligand exhibits promising application prospects in nitro-explosive detection.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056932","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}
Utilizing CO2 for the synthesis of value-added chemicals offers an economically viable route while contributing to reducing greenhouse gas emissions. In this study, three ligands with N2O2 binding sites were designed and used to synthesize mononuclear three cobalt(III) complexes, 1-3, for catalytic activity in the N-formylation reaction. A comparative study was conducted using DMAB as a greener hydrogen donor compared to triethylsilane in the presence of CO2 as a C1 source. All complexes were characterized by UV-Vis, FT-IR, and single-crystal X-ray analysis. Although complex 2 showed the highest activity, all three homogeneous complexes displayed comparable efficiency and were thus employed to develop magnetically separable nanocatalysts for improved recoverability and reusability. Immobilizing the Schiff base complexes onto graphene oxide, Fe3O4, and APTES yielded three magnetically separable GO@Fe3O4@APTES@CoL1/2/3 nanocatalysts. The heterogeneous catalyst obtained from complex 2, i.e., GO@Fe3O4@APTES@CoL2 (GOFeTESCoL2), was catalytically more efficient than the other two. This new heterogeneous magnetically separable nanocatalyst, GOFeTESCoL2, was then characterized by FT-IR, scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, BET analysis, and X-ray photoelectron spectroscopy, which confirmed successful surface modification. GOFeTESCoL2 is magnetically separable and can be reused for six cycles without any loss of catalytic activity or product yield. This reusability offers a cost-effective nonprecious metal-based catalytic approach that minimizes potential reaction losses.
{"title":"N-Formylation of Amines by a Magnetically Separable Cobalt Nanocatalyst Using CO2 as a C1 Source.","authors":"Rimpa Mondal,Sumanta Mondal,Rinku Ghanta,Abani Sarkar,Aratrika Chakraborty,Asim Bhaumik,Tanmay Chattopadhyay","doi":"10.1021/acs.inorgchem.5c05178","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05178","url":null,"abstract":"Utilizing CO2 for the synthesis of value-added chemicals offers an economically viable route while contributing to reducing greenhouse gas emissions. In this study, three ligands with N2O2 binding sites were designed and used to synthesize mononuclear three cobalt(III) complexes, 1-3, for catalytic activity in the N-formylation reaction. A comparative study was conducted using DMAB as a greener hydrogen donor compared to triethylsilane in the presence of CO2 as a C1 source. All complexes were characterized by UV-Vis, FT-IR, and single-crystal X-ray analysis. Although complex 2 showed the highest activity, all three homogeneous complexes displayed comparable efficiency and were thus employed to develop magnetically separable nanocatalysts for improved recoverability and reusability. Immobilizing the Schiff base complexes onto graphene oxide, Fe3O4, and APTES yielded three magnetically separable GO@Fe3O4@APTES@CoL1/2/3 nanocatalysts. The heterogeneous catalyst obtained from complex 2, i.e., GO@Fe3O4@APTES@CoL2 (GOFeTESCoL2), was catalytically more efficient than the other two. This new heterogeneous magnetically separable nanocatalyst, GOFeTESCoL2, was then characterized by FT-IR, scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, BET analysis, and X-ray photoelectron spectroscopy, which confirmed successful surface modification. GOFeTESCoL2 is magnetically separable and can be reused for six cycles without any loss of catalytic activity or product yield. This reusability offers a cost-effective nonprecious metal-based catalytic approach that minimizes potential reaction losses.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"296 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070088","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 : 2026-01-28DOI: 10.1021/acs.inorgchem.5c04793
Tahmina Afroz,David M Freire,Timothy J Hubin,Kayla N Green
Biaryl motifs are central in pharmaceutical drug design, yet conventional synthesis via palladium-catalyzed cross-coupling poses increasing sustainability and cost concerns. The study presented herein explores a greener alternative to palladium using iron(II) complexes supported by tetra-aza macrocyclic ligands for direct arylation of pyrrole with phenylboronic acids. Under aerobic conditions, the optimized [Fe2+L1(Cl)2] complex of ligand Me2Cyclam (L1; 1,8-dimethyl-1,4,8,11-tetraazacyclotetradecane) showed broad substrate compatibility across 23 derivatives, achieving yields up to 66%, and excellent tolerance for functional groups including halides, esters, and strong electron-deficient substituents. Systematic analysis of these results suggests that meta-substitution and mild electron-withdrawing effects favor reactivity, while bulky ortho-steric hindrance suppresses coupling. Mechanistic studies ruled out outer-sphere radical pathways and high-valent iron complexes but do suggest iron(III)-hydroperoxo species as the operative oxidant. Density functional theory (DFT) analysis was carried out on the boronic acid substrates to show that electron-withdrawing substituents enhance the boron electrophilicity and promote the proposed transmetalation step, positioning this step as a key target for mechanistic activation of the substrate. These findings highlight the potential of earth-abundant iron catalysts as sustainable, cost-effective platforms for C-C bond formation in complex molecular scaffolds.
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Pub Date : 2026-01-28DOI: 10.1021/acs.inorgchem.5c05588
Salah-Eddine Bouzarmine,Sohail Ait Jmal,Loubaba Attou,Zineb El Kacemi,Stéphane Mangin,Mohamed Balli
With growing demand for cooling and rising interest in eco-friendly solutions, researchers are focusing on the development of advanced cooling technologies, including those utilizing the magnetocaloric effect by means of magnetocaloric materials. Such development necessitates a thorough understanding of these types of materials. In this context, a density functional theory (DFT) study of neodymium orthophosphate (NdPO4) was conducted by employing the GGA + U + SOC approximation. The compound's electronic and magnetic properties, investigated in the monoclinic monazite structure, revealed an antiferromagnetic configuration, which can be described as two antiparallel sublattices, while electronic structure analysis showed a direct band gap energy of 3.39 eV, indicating an insulating behavior. To probe its magnetic properties, sum rules applied to X-ray magnetic circular dichroism (XMCD) and X-ray absorption spectra (XAS) near the M5,4 edges coupled to pure DFT calculations yielded a total magnetic moment of 1.4 μB, where 2.92, -1.64, and 0.105 μB are the spin, orbital, and dipolar term contributions, respectively. Additionally, NdPO4 shows a modest magneto-crystalline anisotropy with the b-axis identified as the hard and the ac plane as the easy magnetization directions. Finally, the superexchange was found to be very weak; however, it remains the driving mechanism over dipole-dipole interaction, especially between nearest neighbors, while driving the transition temperature around 0.32 K.
随着冷却需求的增长和对环保解决方案的兴趣的增加，研究人员正致力于开发先进的冷却技术，包括通过磁热材料利用磁热效应的技术。这样的发展需要对这些类型的材料有透彻的了解。在此背景下，采用GGA + U + SOC近似对正磷酸钕（NdPO4）进行了密度泛函理论（DFT）研究。在单斜单氮杂石结构中，化合物的电子和磁性表现为反铁磁构型，可以描述为两个反平行的亚晶格，而电子结构分析显示其直接带隙能量为3.39 eV，表明其具有绝缘行为。为了探测其磁性，将x射线磁圆二色性（XMCD）和m5,4边缘附近的x射线吸收光谱（XAS）求和规则与纯DFT计算相结合，得到总磁矩为1.4 μB，其中自旋、轨道和偶极项贡献分别为2.92、-1.64和0.105 μB。此外，NdPO4表现出适度的磁晶各向异性，b轴为硬磁化方向，ac平面为易磁化方向。最后，发现超交换非常弱；然而，它仍然是驱动偶极-偶极相互作用的机制，特别是在最近邻之间，同时驱动0.32 K左右的转变温度。
{"title":"Exploring the Electronic and Magnetic Behavior of NdPO4: A First-Principles Study.","authors":"Salah-Eddine Bouzarmine,Sohail Ait Jmal,Loubaba Attou,Zineb El Kacemi,Stéphane Mangin,Mohamed Balli","doi":"10.1021/acs.inorgchem.5c05588","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05588","url":null,"abstract":"With growing demand for cooling and rising interest in eco-friendly solutions, researchers are focusing on the development of advanced cooling technologies, including those utilizing the magnetocaloric effect by means of magnetocaloric materials. Such development necessitates a thorough understanding of these types of materials. In this context, a density functional theory (DFT) study of neodymium orthophosphate (NdPO4) was conducted by employing the GGA + U + SOC approximation. The compound's electronic and magnetic properties, investigated in the monoclinic monazite structure, revealed an antiferromagnetic configuration, which can be described as two antiparallel sublattices, while electronic structure analysis showed a direct band gap energy of 3.39 eV, indicating an insulating behavior. To probe its magnetic properties, sum rules applied to X-ray magnetic circular dichroism (XMCD) and X-ray absorption spectra (XAS) near the M5,4 edges coupled to pure DFT calculations yielded a total magnetic moment of 1.4 μB, where 2.92, -1.64, and 0.105 μB are the spin, orbital, and dipolar term contributions, respectively. Additionally, NdPO4 shows a modest magneto-crystalline anisotropy with the b-axis identified as the hard and the ac plane as the easy magnetization directions. Finally, the superexchange was found to be very weak; however, it remains the driving mechanism over dipole-dipole interaction, especially between nearest neighbors, while driving the transition temperature around 0.32 K.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"7 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056358","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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