Jie Xu, Meng-Xuan Zuo, Hanyuan Zhang, Zhengyi Di, Cheng-Peng Li
{"title":"A charge-assisted hydrogen-bonded organic framework as host platform for enzymes immobilization and robust biocatalysis","authors":"Jie Xu, Meng-Xuan Zuo, Hanyuan Zhang, Zhengyi Di, Cheng-Peng Li","doi":"10.1039/d4qi03044c","DOIUrl":"https://doi.org/10.1039/d4qi03044c","url":null,"abstract":"In situ encapsulation of enzymes into hydrogen-bonded organic frameworks (HOFs) offers a promising strategy to enhance enzyme durability and activity recovery in biocatalysis. In this study, we report the immobilization and stabilization of catalase (CAT) and α-amylase (α-Amy) using a novel charge-assisted HOF, TNU-14. This HOF is constructed from tiramidinium and tricarboxylate building blocks under ambient conditions. Benefiting from the electrostatic interactions between the negatively charged enzyme surfaces and the positively charged tiramidinium units, the TNU-14 exoskeleton forms around the enzymes within 15 minutes. As a result, TNU-14 effectively protects the enzymes from degradation while maintaining their activity under harsh chemical and physical conditions, including acidic or alkaline environments, proteolytic enzyme trypsin, chaotropic agent urea, high temperatures, and through at least ten catalysis/filtration cycles. This study represents the first demonstration of a charge-assisted HOF scaffold assembled from trigonal building blocks for enzyme immobilization, paving the way for developing a toolset for enzyme and protein carriers.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhuolin Shi, Yuwen Wang, Rong Zhang, Hanshu Li, Rui Cai, Jinguo Wu, Xin Wang, Hechuan Li, Xuezhao Li, Cheng He
{"title":"Confining Cu(I) Ions within an Ir(III)-Based Twin-Cavity Cage for Photo-Triggered Dioxygen Activation toward C(sp³)−H Oxidation.","authors":"Zhuolin Shi, Yuwen Wang, Rong Zhang, Hanshu Li, Rui Cai, Jinguo Wu, Xin Wang, Hechuan Li, Xuezhao Li, Cheng He","doi":"10.1039/d5qi00091b","DOIUrl":"https://doi.org/10.1039/d5qi00091b","url":null,"abstract":"Efficient dioxygen (O2) activation under mild and environmentally friendly conditions remains a challenging yet crucial research area in chemistry. In this study, by rationally modulating the coordination environment of Cu(I) ions and integrating a photoactive Ir(III) module into a supramolecular system, we introduce a simple yet effective approach for O2 activation (O2→1O2→O2•-) under LED irradiation (450 nm), leading to efficient C(sp3)−H photo-oxidation of N-aryl tetrahydroisoquinolines. The hexaformyl end-capped fac-Ir(ppy)₃ module (1), Ir(III)-based twin-cavity cage (2), and the supramolecular Cu2@2 entity—where two Cu(I) ions are coordinated within cage 2—were comprehensively characterized using NMR, HR-MS, and X-ray crystallography. The confined cavities of 2 effectively trap Cu(I) ions, shielding them from oxidation by O₂. However, mechanistic studies reveal that the photoinduced singlet oxygen (¹O₂) generated from the fac-Ir(ppy)₃ module could activate Cu(I), facilitating the generate superoxide radical (O2•-) species. Importantly, the regeneration of the Cu(I) active redox state can be accomplished through electron transfer from the photoactive *Ir(III) to the resulting Cu(II) ions. This study introduces a gradual and controlled energy/electron delivery process from Ir(III) module to O2 and the Cu centres, offering an advanced supramolecular strategy for visible light-induced O2 activation in oxidation reactions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wenjing Guo, Xiao Sun, Wenkang Cheng, Guoyong Chen, Ying Wei, Zhenhong Wei, Hu Cai
{"title":"Ferroelectric Crystals with Naphthenic Hydrocarbon-Modified Carborane Vertices","authors":"Wenjing Guo, Xiao Sun, Wenkang Cheng, Guoyong Chen, Ying Wei, Zhenhong Wei, Hu Cai","doi":"10.1039/d4qi03172e","DOIUrl":"https://doi.org/10.1039/d4qi03172e","url":null,"abstract":"In this study, we present the first synthesis of ferroelectric crystals where the carbon vertices of carboranes are substituted with cycloalkane groups. These crystals include 1,2-(1,3-propanediyl)-o-carborane (1) and 1,2-(1,4-hexanediyl)-o-carborane (2), both of which exhibit relatively high curie temperatures at 328.6 K and 320.6 K. Notably, to the best of our knowledge, this represents the first instance of ferroelectric crystals derived from modifications at the carbon vertex of carborane. This discovery provides a valuable new avenue for research into novel carborane-based ferroelectrics and holds promise for advancing the broader application of ferroelectric materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"40 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055623","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A three-dimensional lead iodide-bromide perovskitoid with distinct photoelectric anisotropy","authors":"Zixian Yu, Kuan Kuang, Jie Yang, Junyuan Duan, Mingkai Li, Yunbin He, Junnian Chen","doi":"10.1039/d4qi03073g","DOIUrl":"https://doi.org/10.1039/d4qi03073g","url":null,"abstract":"Three-dimensional (3D) hybrid perovskitoids have shown immense potential in optoelectronic applications. However, it is still challenging to achieve photoelectric anisotropy in 3D perovskitoids. Herein, we report a 3D (NMPDA)Pb<small><sub>2</sub></small>I<small><sub>4</sub></small>Br<small><sub>2</sub></small> (NMPDA = <em>N</em>-methyl propane diammonium) perovskitoid with strong anisotropic merits, achieved by the incorporation of Br<small><sup>−</sup></small> ions. The preferential distribution of Br<small><sup>−</sup></small> ions at the edge-sharing halide sites triggers distinct structural anisotropy, balanced distortion and microstrain relaxation. The structural anisotropy yields a highly anisotropic band structure, which enables remarkable charge transport anisotropy, with the [001] direction enabling higher carrier mobility and longer carrier diffusion length than the [010] direction. Consequently, the 3D (NMPDA)Pb<small><sub>2</sub></small>I<small><sub>4</sub></small>Br<small><sub>2</sub></small> single crystal manifests a responsivity and detectivity of 0.40 A W<small><sup>−1</sup></small> and 4.85 × 10<small><sup>12</sup></small> Jones, respectively, along the preferred [001] direction, which are orders of magnitude larger compared to the [010] direction, and outperforms the reported 3D perovskitoids. Moreover, the (NMPDA)Pb<small><sub>2</sub></small>I<small><sub>4</sub></small>Br<small><sub>2</sub></small> single crystal device shows a sensitive response to polarized light, involving a responsivity and detectivity of 1.07 A W<small><sup>−1</sup></small> and 7.05 × 10<small><sup>12</sup></small> Jones, respectively. These observations offer novel insights into the development of 3D perovskitoids toward advanced optoelectronic devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"5 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055606","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dana Josa, Piedad Herrera-Ramírez, Xiao Feng, Albert Gutiérrez, David Aguilà, A. Grabulosa, Manuel Martínez, Kogularamanan Suntharalingam, Patrick Gamez
{"title":"Cyclometalated half-sandwich iridium(III) and rhodium(III) complexes as efficient agents against cancer stem-cell mammospheres","authors":"Dana Josa, Piedad Herrera-Ramírez, Xiao Feng, Albert Gutiérrez, David Aguilà, A. Grabulosa, Manuel Martínez, Kogularamanan Suntharalingam, Patrick Gamez","doi":"10.1039/d4qi02763a","DOIUrl":"https://doi.org/10.1039/d4qi02763a","url":null,"abstract":"Four cyclometalated complexes, namely [IrCl(5-pentamethylcyclopendadienyl)(k2C-diphenyl(1-pyrenyl)phosphane)] (1) and [RhCl(5-pentamethylcyclopendadienyl)(k2C-diphenyl(1-pyrenyl)phosphane)] (2), and their DMSO-coordinated counterparts [Ir(η5-pentamethylcyclopendadienyl)(kS-dmso)(k2C-diphenyl(1-pyrenyl)phosphane)]PF6 (1·DMSO) and [Rh(η5-pentamethylcyclopendadienyl)(kS-dmso)(k2C-diphenyl(1-pyrenyl)phosphane)]PF6 (2·DMSO), were synthesized and fully characterized, including their single-crystal X-ray structures. DNA-interacting 1 and 2 exhibits IC50 values in the range 0.53–0.79 µM against bulk breast cancer cells and breast cancer stem cells (CSCs), i.e., HMLER and HMLER-shEcad cells. The complexes are up to seven times more active than salinomycin and up to nine times more active than cisplatin. Moreover, 1 and 2 are very effective (in the micromolar range) against mammospheres obtained from single cell suspensions of HMLER-shEcad cells, 1 being thrice more toxic than 2 and up to 4.5-fold more potent than cisplatin and salinomycin. In depth mechanistic studies revealed that 1 induces necrosis, which is potentially dependent on necrosome formation and independent of ROS concentration. The efficacy of 1 against breast CSCs can be enhanced by co-treatment with PARP-1 inhibitors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050588","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jun-Wen Xu, Lawrence Cho-Cheung Lee, Alex Man-Hei Yip, Guang-Xi Xu, Peter Kam-Keung Leung, Kenneth Kam-Wing Lo
{"title":"Luminescent iridium(III) 2-cyanobenzothiazole complexes as site-specific labels to afford peptide-based phosphorogenic probes and hydrogels for enzyme activity sensing, cancer imaging and photodynamic therapy","authors":"Jun-Wen Xu, Lawrence Cho-Cheung Lee, Alex Man-Hei Yip, Guang-Xi Xu, Peter Kam-Keung Leung, Kenneth Kam-Wing Lo","doi":"10.1039/d4qi03276d","DOIUrl":"https://doi.org/10.1039/d4qi03276d","url":null,"abstract":"Site-specific modification of biomolecules is crucial to the development of functional constructs for biomedical applications, offering precise control over the number and location of the functional handles incorporated. In this work, we designed, synthesised and characterised three luminescent cyclometallated iridium(III) complexes bearing a 2-cyanobenzothiazole (CBT) moiety [Ir(N^C)2(bpy-CBT)](PF6) (HN^C = 2-(2,4-difluorophenyl)pyridine (Hdfppy) (1), 2-phenylpyridine (Hppy) (2), methyl 2-phenyl-4-quinolinecarboxylate (Hpqe) (3); bpy-CBT = 4-(2-cyanobenzo[d]thiazol-6-yl)oxymethyl-4’-methyl-2,2’-bipyridine) as site-specific labels for N-terminal cysteine (NCys). These complexes displayed high reactivity and selectivity towards NCys, enabling facile peptide conjugation via the CBT–NCys condensation reaction. Complex 2 was used to prepare a peptide-based phosphorogenic probe 2-MMP-QSY7 for matrix metalloproteinase-2/9 (MMP-2/9) activity sensing and photocytotoxic applications. The conjugate showed substantial emission enhancement (I/Io = 9.8) in the presence of MMP-2/9, which allowed for the sensitive detection of MMP-2/9 activity in live cells and the facile differentiation of cancer and normal cells. The conjugate also exhibited controllable singlet oxygen generation and thereby photocytotoxicity in these cell lines. Additionally, complex 2 was utilised to fabricate two types of hydrogels: a non-biodegradable hydrogel Gel-1 as a cell culture scaffold integrated with MMP-2/9 sensing capability for examining the enzyme activity in 3D cell culture; and a biodegradable hydrogel Gel-2 as an MMP-2/9-sensitive carrier for selective delivery of luminescent iridium(III) complexes into cancer cells for imaging and photocytotoxic applications. The results of this work will contribute to the development of site-specific bioconjugation reagents with interesting photophysical properties, facilitating the construction of photofunctional peptide conjugates and biomaterials for biosensing, bioimaging, PDT and drug delivery applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"50 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Oxygen-Coordinated MOF Membrane Facilitated Construction of Supported Co2P/CoP@C Heterostructures for Water Electrolysis","authors":"Chongxi Zhang, Fengting Li, Dong Wu, Qingmeng Guo, Zhanning Liu, Zhikun Wang, Zixi Kang, Lili Fan, Daofeng Sun","doi":"10.1039/d4qi03103b","DOIUrl":"https://doi.org/10.1039/d4qi03103b","url":null,"abstract":"Integration of cobalt phosphides (Co2P and CoP) in carbon matrix shows great promise for developing high-performance catalysts for water electrolysis. Nevertheless, the control synthesis of these two phases with effective interface, uniform dispersion, and simplified synthesis process are still challenging. Herein, we proposed a strategy that involves pre-construction of Co/CoO@C heterostructure followed by post-conversion by phosphorization to achieve the precise synthesis of Co2P/CoP@C heterostructure, which was realized by utilizing MOF as the self-sacrificial template. The oxygen-coordinated MOF that shows advantages in building Co/CoO heterostructure and further conversion to phosphides was employed in this work and grown into a high-quality membrane via cathodic electrodeposition on the graphite substrate (Gss). The obtained catalyst (Gss-Co2P/CoP@C-800) requires 146 and 365 mV overpotentials to reach a current density of 100 mA cm-2 for HER and OER respectively, and 1.54 V to reach current density of 10 mA cm-2 for water electrolysis. Beyond the significantly enhanced conductivity that originates from the robust interaction between MOF and Gss, the establishment of effective Co2P/CoP interface also plays a pivotal role in contributing to the high performance of Gss-Co2P/CoP@C-800. As revealed by density functional theory (DFT) calculations, the unique d-orbital electron distribution of Co2P/CoP and the enhanced state density near the Fermi level facilitate its efficient electron transport and renders the Co2P/CoP heterostructure region a crucial active site for water electrolysis. This study would provide new insights into the rational design and construction of heterostructures based on MOFs for efficient and green energy conversions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hong Ding, Tiantian Li, Chengyu Liu, Jiali Wang, Tengfei Zhang, Long Chen, Haijiao Xie, Gang Wang, Tiantian Gu
{"title":"Layered vanadium oxide with tunable layer spacing via dual organic molecule co-insertion for advanced aqueous zinc-ion batteries","authors":"Hong Ding, Tiantian Li, Chengyu Liu, Jiali Wang, Tengfei Zhang, Long Chen, Haijiao Xie, Gang Wang, Tiantian Gu","doi":"10.1039/d4qi02689f","DOIUrl":"https://doi.org/10.1039/d4qi02689f","url":null,"abstract":"The narrow layer spacing of layered vanadium pentoxide (α-V<small><sub>2</sub></small>O<small><sub>5</sub></small>) and the slow diffusion kinetics of Zn<small><sup>2+</sup></small> limit its application in aqueous zinc-ion batteries. The organic molecule pre-insertion strategy has been proposed to improve its electrochemical performance. Nevertheless, the embedding of electrochemically inert organic molecules leads to a decrease in the volume-specific capacity. Here, a bi-organic molecular co-insertion strategy is proposed by introducing electrochemically active cyclohexanehexone octahydrate (KCO) and 1-methyl-2-pyrrolidone (NMP) into α-V<small><sub>2</sub></small>O<small><sub>5</sub></small> to obtain different spacings of α-V<small><sub>2</sub></small>O<small><sub>5</sub></small> (11.93, 11.77, 11.06, 8.76, and 7.67 Å) and optimize electrochemical properties by spacing. Furthermore, experiments and DFT calculations reveal that co-insertion provides additional active sites (C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O/C–O), enhances electrical conductivity, and reduces desolvation energy, thus leading to superior zinc storage properties. Thus, benefiting from the collaborative effect of the bi-organic molecules and the suitable layer spacing, VNK4 (8.76 Å) possesses the best electrochemical performance with a 95.7% capacity retention over 100 cycles at 0.5 A g<small><sup>−1</sup></small> and a specific capacity of up to 190.6 mA h g<small><sup>−1</sup></small> over 9500 cycles at 10 A g<small><sup>−1</sup></small>. This work offers a novel thought for constructing the organic–inorganic hybrid cathode.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"61 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yifu Zhang, Xianfang Tan, Xiaoyu Pei, Yang Wang, Shengping Yi, Qiushi Wang, Xiaoming Zhu, Changgong Meng, Chi Huang
{"title":"Multiple Interfaces Coupling Triggered Built-in Electric Field over Double-Sandwiched RGO/Cobalt silicate/Cobalt-Iron Phosphide for Improving Overall Water-Splitting Performance","authors":"Yifu Zhang, Xianfang Tan, Xiaoyu Pei, Yang Wang, Shengping Yi, Qiushi Wang, Xiaoming Zhu, Changgong Meng, Chi Huang","doi":"10.1039/d4qi02987a","DOIUrl":"https://doi.org/10.1039/d4qi02987a","url":null,"abstract":"The exploration of efficient and durative bifunctional electrocatalysts for overall water splitting (OWS) is critical for hydrogen production in clean energy applications. Herein, a novel double-sandwiched architecture of reduced graphene oxide (rGO), cobalt silicate (CS), and cobalt-iron phosphides, denoted as rGO/CS/(Co,Fe)xPy, is designed to enhance both oxygen evolution reaction (OER) and hydrogen ER (HER) in alkaline media. The formation of Co2P and Fe2P on rGO/CS not only protects the silicate from alkaline corrosion but also generates dual-active centers that synergistically improve conductivity and catalytic activity. Multiple interface coupling between rGO, CS, and (Co,Fe)xPy triggers a built-in electric field, which significantly enhances charge separation, electron transport, and reaction kinetics. This built-in electric field lowers the energy barrier for HER by facilitating H-OH bond dissociation and accelerates OER by promoting OH⁻ adsorption. The rGO/CS/(Co,Fe)xPy catalyst achieves overpotentials of 256 mV (OER) and 180 mV (HER) at 10 mA·cm–2, surpassing most reported catalysts and rivaling commercial Pt/C and RuO2. Furthermore, the rGO/CS/(Co,Fe)xPy (+/-) demonstrates a low OWS voltage of 1.41 V. The current work provides a new approach to catalyst design through interface engineering and electric field optimization, offering a scalable solution for sustainable hydrogen production.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"108 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yan Yan Grisan Qiu, Simone Mearini, Daniel Baranowski, Iulia Cojocariu, Matteo Jugovac, Giovanni Zamborlini, Pierluigi Gargiani, S. Manuel Valvidares, Vitaliy Feyer, Claus M. Schneider
{"title":"Robust high-spin Fe2+ centers in 2D TCNQ-based metal-organic frameworks","authors":"Yan Yan Grisan Qiu, Simone Mearini, Daniel Baranowski, Iulia Cojocariu, Matteo Jugovac, Giovanni Zamborlini, Pierluigi Gargiani, S. Manuel Valvidares, Vitaliy Feyer, Claus M. Schneider","doi":"10.1039/d4qi03123g","DOIUrl":"https://doi.org/10.1039/d4qi03123g","url":null,"abstract":"Two-dimensional metal-organic frameworks (2D MOFs) are atomically thin materials that combine the properties of organic molecules with the structural characteristics of crystalline inorganic solids. Their unique magnetic and electronic properties arise from the interaction between transition metal centers and organic linkers. This study focuses on the high-spin Fe²⁺ centers in a 7,7,8,8-tetracyanoquinodimethane (TCNQ)-based 2D MOF, where hybridization between Fe 3d states and π-symmetric orbitals of TCNQ ligands stabilizes regularly spaced magnetic centers. X-ray magnetic circular dichroism (XMCD) measurements confirm the robustness of these magnetic properties across various substrates, including graphene and gold.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"6 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143031187","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}