Inorganic Chemistry最新文献_第9页

DFT Elucidationof the Mechanism and Origins of Regio-and Stereoselectivity in Visible Light-Mediated Pd-Catalyzed 1,4-Aminoalkylationof 1,3-Dienes 可见光介导的pd催化1,3-二烯的1,4-氨基烷基化反应中区域和立体选择性的机制和来源的DFT研究

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-17 DOI: 10.1021/acs.inorgchem.6c03921

Yanhong Liu,Tong Zheng,Yiding Dong,Qingfeng Hou,Dongju Zhang

{"title":"DFT Elucidation\u0000of the Mechanism and Origins of Regio-\u0000and Stereoselectivity in Visible Light-Mediated Pd-Catalyzed 1,4-Aminoalkylation\u0000of 1,3-Dienes","authors":"Yanhong Liu,Tong Zheng,Yiding Dong,Qingfeng Hou,Dongju Zhang","doi":"10.1021/acs.inorgchem.6c03921","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03921","url":null,"abstract":"Abstract We report a comprehensive DFT and TD-DFT investigation of the mechanism underlying the photosensitizer-free visible light-mediated palladium-catalyzed 1,4-aminoalkylation of 1,3-dienes with alkyl N-hydroxyphthalimide (NHP) redox-active esters, with particular emphasis on elucidating the catalytic cycle and the origins of the experimentally observed regio- and stereoselectivities. Our calculations reveal that the reaction proceeds through a Pd0/PdI/PdII/Pd0 catalytic cycle rather than the previously proposed Pd0/PdI/Pd0 pathway. TD-DFT calculations identify (PPh3)4Pd0, rather than the Pd0-diene complex, as the endogenous photosensitizer responsible for visible-light absorption and subsequent single-electron transfer (SET). The NHP ester plays dual roles by serving both as the alkyl radical precursor and as the nitrogen source for subsequent C–N bond formation. The C–N bond-forming step proceeds through an outer-sphere nucleophilic attack of the phthalimide anion on an η3-π-allylpalladium(II) complex rather than via inner-sphere reductive elimination, and this process is identified as the regio- and stereoselectivity-determining step. Distortion–interaction and energy decomposition analyses quantitatively account for the excellent regio- and stereoselectivities observed experimentally. These findings provide a comprehensive mechanistic picture of this visible light-mediated Pd catalysis and offer valuable insights for the rational design of related photochemical palladium-catalyzed transformations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210050","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}

引用次数: 0

Regium Bondingto Carbones: Transition to Covalencyand σ/π Lone Pair Selectivity 与碳原子成键：向共价过渡和σ/π孤对选择性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-17 DOI: 10.1021/acs.inorgchem.6c04366

Hangyu Zhou,Qianxin Zhou,Qian Peng,Steve Scheiner

{"title":"Regium Bonding\u0000to Carbones: Transition to Covalency\u0000and σ/π Lone Pair Selectivity","authors":"Hangyu Zhou,Qianxin Zhou,Qian Peng,Steve Scheiner","doi":"10.1021/acs.inorgchem.6c04366","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04366","url":null,"abstract":"Abstract Carbones possess two carbon-centered lone pairs of approximately σ and π character, but the factors governing their selective engagement with a Lewis acid remain poorly understood. Here, AuCN is employed as a compact regium bond Lewis acid to probe the electronic and geometric preferences of a series of carbones, unsaturated carbon bases, and conventional carbene C(NH2)2. DFT calculations reveal exceptionally strong and highly directional regium bonds. The four amine-supported carbones exhibit BSSE-corrected interaction energies with AuCN of approximately −100 kcal mol–1 and undergo pronounced pyramidalization around the central carbon, identifying the out-of-plane π-type lone pair as the preferred donor. In contrast, carbones containing unsaturated N substituents, phosphines, or carbene C(NH2)2 engage AuCN through an in-plane σ-type lone pair. Electrostatic and orbital terms contribute almost equally to stabilization, accompanied by substantial charge transfer, partial shared-electron character, and weakening of the Au–C(CN) bond within the AuCN fragment. The results reveal ligand-dependent variations in Au–C(carbone) interaction strength and covalent character within a continuous bonding framework.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210052","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}

引用次数: 0

Hammett-DrivenSecondary Ligand Effects Control Geometryand Electronic Structure of 5-Substituted Copper(II)–CytosineComplexes 汉米特驱动的二次配体效应控制5-取代铜(II) -细胞素配合物的几何和电子结构

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-17 DOI: 10.1021/acs.inorgchem.6c03215

Harahng Lee,Abhinav Sai Chalasani,Hengrui Chen,Jake Bailey,Edward Njoo

{"title":"Hammett-Driven\u0000Secondary Ligand Effects Control Geometry\u0000and Electronic Structure of 5-Substituted Copper(II)–Cytosine\u0000Complexes","authors":"Harahng Lee,Abhinav Sai Chalasani,Hengrui Chen,Jake Bailey,Edward Njoo","doi":"10.1021/acs.inorgchem.6c03215","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03215","url":null,"abstract":"Abstract Metal-nucleobase interactions play central roles in biological chemistry and metal-based therapeutic design, yet the influence of nucleobase substitution on coordination geometry and thermodynamic stability remains underexplored. Herein, we report the systematic investigation of copper(II) complexes of 5-substituted cytosine ligands, specifically [Cu(XCyt)4](OTf)2, where X = H, F, Cl, or I, designed to isolate the effect of a C5 halogen substitution on ligand–metal interactions. Characterization was accomplished via solution-state UV–vis, Fourier transform infrared (FT-IR) spectroscopy, 1H NMR spectroscopy, fluorescence spectroscopy, elemental analysis, and single-crystal X-ray diffraction spectroscopy. Single crystal X-ray diffraction reveals that C5 substitution has minimal impact on Cu···N bond distances, but induces pronounced, substituent-dependent changes in coordination geometry. Specifically, increasing substituent σpara Hammett constants lower the Lewis basicity of the cytosine carbonyl and appear to perturb Cu···O interactions and interligand hydrogen bonding, with a concomitant increase in the planarity of the CuN4 coordination environment. These correlate with systematic changes in electronic structure, as evidenced by linear shifts in UV–visible absorption and corresponding trends in paramagnetic relaxation behavior measured by 1H NMR spectroscopy. Collectively, these results demonstrate that substitution at the C5 position modulates metal-centered properties primarily through secondary-sphere interactions, rather than direct perturbation of metal–ligand bonding, which in turn drives linear perturbations of UV–vis absorbance spectra and paramagnetic relaxation properties.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"30 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210051","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}

引用次数: 0

ElectroabsorptionSpectroscopy of BOPHY Derivatives:Probing Charge-Transfer Character in the Excited State BOPHY衍生物的电吸收光谱：探测激发态中的电荷转移特征

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-17 DOI: 10.1021/acs.inorgchem.6c03488

Md Bulu Rahman,Victoria Villarreal,Dijo Prasannan,Victor N. Nemykin,Toshifumi Iimori

{"title":"Electroabsorption\u0000Spectroscopy of BOPHY Derivatives:\u0000Probing Charge-Transfer Character in the Excited State","authors":"Md Bulu Rahman,Victoria Villarreal,Dijo Prasannan,Victor N. Nemykin,Toshifumi Iimori","doi":"10.1021/acs.inorgchem.6c03488","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03488","url":null,"abstract":"Abstract BOPHYs are excellent fluorophores exhibiting high fluorescence quantum yield, strong visible light absorption, tunable emission colors, controllable electron-accepting properties, and high photostability. These properties make BOPHYs attractive as potential nonfullerene electron acceptors (NFAs). Recent studies on Y6, a benchmark NFA, have collectively suggested that charge-transfer character in the excited state promotes efficient charge generation. Here, the charge-transfer character in the excited state of a series of BOPHYs is investigated using electroabsorption and Stark fluorescence spectroscopies. Methyl-substituted, ester- and phenyl-substituted, and pyridone-fused BOPHYs are comparatively studied. Fluorescence quantum yield was reduced in the presence of electric fields, which was attributed primarily to an enhancement of intramolecular nonradiative deactivation processes. Time-dependent density functional theory (TD-DFT) calculations and analyses of electron density redistribution induced by photoexcitation indicate that molecular symmetry determines the patterns of local charge redistribution and consequently, the magnitude of the net dipole moment change (|μ|). Among the three derivatives, pyridone-fused BOPHY exhibits the largest |μ| upon photoexcitation. These results indicate that the lowest excited state of pyridone-fused BOPHY has substantial intramolecular charge-transfer character. This study provides a basis for the functionalization of BOPHY for future photovoltaic and organic optoelectronic applications in addition to the conventional π-conjugation extension approach.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210053","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}

引用次数: 0

FluorinatedArylethynyl Substituents in Zn(II) Complexesof Azadipyrromethene Guide Self-Assembly in Crystals 氮杂二吡咯甲烷锌（II）配合物中的氟化芳基取代基引导晶体自组装

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-16 DOI: 10.1021/acs.inorgchem.6c03689

David A. Raufman,Neha Jadhav,Shashika A. Arachchige,Lexi R. Knight,Jayvic C. Jimenez,Geneviève Sauvé

{"title":"Fluorinated\u0000Arylethynyl Substituents in Zn(II) Complexes\u0000of Azadipyrromethene Guide Self-Assembly in Crystals","authors":"David A. Raufman,Neha Jadhav,Shashika A. Arachchige,Lexi R. Knight,Jayvic C. Jimenez,Geneviève Sauvé","doi":"10.1021/acs.inorgchem.6c03689","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03689","url":null,"abstract":"Abstract Zn(II) complexes of 2,8-arylethynyl 1,3,7,9-tetraphenyl azadipyrromethenes are promising molecular semiconductors with strong visible-NIR absorption and a nonplanar distorted tetrahedral geometry around the Zn(II) center, but their charge transport properties are limited by the orientation and strength of intermolecular π–π stacking interactions. To optimize their intermolecular π–π stacking interactions, we explored substitution of the pyrrolic phenylethynyl groups in Zn(L1)2 at the phenyl meta positions with either fluorines (Zn(L1-m-2F)2) or trifluoromethyls (Zn(L1-m-2CF3)2). Fluorination had minimal effects on optical properties and slightly deepened frontier orbital energy levels. On the other hand, fluorination strongly affected the complexes’ molecular packing: while Zn(L1-m-2F)2 had the same C2/c space group as Zn(L1)2, the −CF3 groups in Zn(L1-m-2CF3)2 promoted a higher ordered space group of Fddd. Further, in Zn(L1)2 and Zn(L1-m-2F)2, the phenylethynyl groups stack with the core phenyls of neighboring molecules, whereas in Zn(L1-m-2CF3)2, the bis(trifluoromethyl)-substituted phenylethynyl groups of neighboring molecules stack with each other with a shorter π–π stacking distance than in the other two molecules. Computations revealed that fluorination decreases the internal reorganization energy for electron transfer and increases overlap integrals for charge transfer. Fluorination is thus a promising strategy to tune molecular packing and parameters relevant to charge transport.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210056","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}

引用次数: 0

Xanthate-BasedCustomizable Fluorescent/Non-FluorescentMacrocycles: Design, Synthesis, Photophysical Modulation, and TailoringSilver Nanoparticle 基于黄药的可定制荧光/非荧光大循环：设计，合成，光物理调制和剪裁纳米银颗粒

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-16 DOI: 10.1021/acs.inorgchem.6c03929

Debashis Barik,Gadha Rajesh,Fathima Nida P S R,Mintu Porel

{"title":"Xanthate-Based\u0000Customizable Fluorescent/Non-Fluorescent\u0000Macrocycles: Design, Synthesis, Photophysical Modulation, and Tailoring\u0000Silver Nanoparticle","authors":"Debashis Barik,Gadha Rajesh,Fathima Nida P S R,Mintu Porel","doi":"10.1021/acs.inorgchem.6c03929","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03929","url":null,"abstract":"Abstract Macrocycles, with tunable ring sizes and versatile functional groups, are garnering significant interest for their extensive applications in material and biomedical science. Herein, an effort was made to synthesize metal-free, xanthate-based tunable macrocycles. The mild reaction conditions, along with the versatile tunability of functional groups, render this synthetic strategy highly efficient. Subsequent to the synthesis, the macrocycles were comprehensively characterized by liquid chromatography-mass spectrometry (LC-MS), 1H NMR, 1H–1H correlation spectroscopy (COSY) NMR, and 13C NMR. The synthesis of macrocycles yields between 40 and 50%. The macrocycles were tailored in terms of hydrophilicity–hydrophobicity and fluorescence properties by varying the backbone and fluorophore side chains. As a proof of concept, the macrocycles were employed as capping agents for silver nanoparticles, where they effectively stabilized the nanoparticles, tuned their properties, and significantly enhanced their catalytic activity. These findings demonstrate that this class of macrocycles can be readily integrated with various secondary systems to tune and optimize their physicochemical and functional properties.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"50 3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210055","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}

引用次数: 0

MechanisticInsights into Palladium-Catalyzed 1,4-Hydrofunctionalizationof 1,3-Enynes through a Coordination-Induced Orbital PolarizationFramework 通过配位诱导的轨道极化框架对钯催化1,4- 1,3-炔的氢化功能化的机理研究

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c03742

Shan Wang,Kaiqi Huang,Tilong Yang,Zhihui Shao,Zheng Wang

{"title":"Mechanistic\u0000Insights into Palladium-Catalyzed 1,4-Hydrofunctionalization\u0000of 1,3-Enynes through a Coordination-Induced Orbital Polarization\u0000Framework","authors":"Shan Wang,Kaiqi Huang,Tilong Yang,Zhihui Shao,Zheng Wang","doi":"10.1021/acs.inorgchem.6c03742","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03742","url":null,"abstract":"Abstract Palladium-catalyzed 1,4-hydrofunctionalization of 1,3-enynes provides a powerful and atom-economical approach to multisubstituted allenes. Despite extensive synthetic developments, the fundamental origin of activation mode selection and regioselectivity in these transformations remains elusive. Herein, we propose a coordination-induced orbital polarization (CIOP) framework that describes how established metal–substrate orbital interactions associated within different Pd coordination environments generate distinct site-dependent redistributions of frontier-orbital character across the conjugated enyne π-system. These electronic responses provide a common basis for rationalizing activation mode selection and regioselectivity. The applicability of the CIOP framework was examined through density functional theory investigations of Pd-catalyzed hydroboration, hydroamination, and hydrosilylation. Across all three reaction classes, the calculated orbital polarization patterns were consistent with the experimentally observed activation pathways and site selectivities. These findings support CIOP as a unified interpretative framework for relating metal coordination, enyne electronic structure, and catalytic divergence across the Pd-catalyzed hydrofunctionalization reactions examined in this study.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210109","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}

引用次数: 0

Role of Extrinsic Doping of Mg2+ on Crystallographicand Morphological Transition in CdO Nanoparticles under Acoustic ShockedConditions 外源掺杂Mg2+对声冲击条件下CdO纳米颗粒晶体和形态转变的影响

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c03645

Sivakumar Aswathappa,Lidong Dai,Sahaya Jude Dhas Sathiyadhas,Cathrin Lims Selvakumar,Raju Suresh Kumar,Haiying Hu,Muthu Devaraj,Weixiang Kong,Qinghang Tang

{"title":"Role of Extrinsic Doping of Mg2+ on Crystallographic\u0000and Morphological Transition in CdO Nanoparticles under Acoustic Shocked\u0000Conditions","authors":"Sivakumar Aswathappa,Lidong Dai,Sahaya Jude Dhas Sathiyadhas,Cathrin Lims Selvakumar,Raju Suresh Kumar,Haiying Hu,Muthu Devaraj,Weixiang Kong,Qinghang Tang","doi":"10.1021/acs.inorgchem.6c03645","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03645","url":null,"abstract":"Abstract The role of extrinsic dopants in acoustic shock wave-induced phase transitions of solids remains unclear. Herein, we report the crystallographic structural stability of the Mg-doped CdO nanoparticles under acoustic shocked conditions to understand how extrinsic doping of Mg2+ manipulates the critical pressure for the B1–B2 transition compared to pure CdO NPs. From the XRD results, Mg-CdO remains stable in the B1 phase at 200 shocks, whereas the B1–B2 transition occurs in pure CdO at 200 shocks. Even in the absence of structural transitions, sphere-to-hexagonal honeycomb morphological changes are observed, which bring some considerable modifications in the vibrational, optical, and magnetic properties of the Mg-CdO NPs. The values of optical band gap energy are determined as 2.30, 2.23, and 2.22 eV for 0, 100, and 200 shocks, respectively, and the saturation magnetization values are found to be 0.14, 0.33, and 0.14 emu/g for 0, 100, and 200 shocks, respectively. The observed findings demonstrate that the presence of Mg2+ enhances the critical pressure for the B1–B2 transition compared to pure CdO. Moreover, the observed morphological changes are discussed based on the shock wave-induced thermal conductivity-driven superheating concepts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210057","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}

引用次数: 0

Flexible TransparentScintillation Films Based onChiral Molecular Scintillators Showing Strong Circularly PolarizedLuminescence and High-Resolution X-ray Imaging 基于手性分子闪烁体的柔性透明闪烁膜具有强圆偏振发光和高分辨率x射线成像

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c04645

Li-Hong Tan,Si-En Yin,Jia-Ran Shi,Jun-Jie Hu,Zhao-Bo Hu,He-Rui Wen

{"title":"Flexible Transparent\u0000Scintillation Films Based on\u0000Chiral Molecular Scintillators Showing Strong Circularly Polarized\u0000Luminescence and High-Resolution X-ray Imaging","authors":"Li-Hong Tan,Si-En Yin,Jia-Ran Shi,Jun-Jie Hu,Zhao-Bo Hu,He-Rui Wen","doi":"10.1021/acs.inorgchem.6c04645","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c04645","url":null,"abstract":"Abstract Flexible scintillation films based on chiral molecular scintillators have considerable potential for application in advanced technologies, such as three-dimensional displays, optical information storage, and high-resolution diagnostic imaging. Herein, a pair of chiral Cd–Tb complex enantiomers [(R, R)/(S, S)-(L)2TbCd2(H2O)4] (ClO4)3 (R/S –Cd-Tb) was synthesized, and they exhibit a high PLQY of 38.40% and strong circularly polarized luminescence (CPL) with asymmetry factors of 4.69 × 10–2. R/S –Cd-Tb has strong X-ray scintillation performance with a light yield of 2136 and 2111 ph·MeV–1 based on LuAG:Ce and the X-ray detection limit of 50.6 and 52.1 nGy·s–1, respectively. Chiral flexible transparent scintillation films of R/S –Cd-Tb@PMMA were prepared using R/S –Cd-Tb, and the asymmetry factor of the R/S –Cd-Tb@PMMA film is 2.4 × 10–2. The R/S –Cd-Tb@PMMA film exhibits strong circularly polarized radioluminescence (CPRL) and circularly polarized light-emitting diode emission (CP-LEDs). Moreover, it can deliver prominent CPRL signals and achieve high-resolution X-ray imaging with a spatial resolution of 23.96 lp/mm. The results indicate that chiral lanthanide complexes represent a promising class of chiral molecular scintillator materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"292 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210058","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}

引用次数: 0

Comprehensive Investigation of Structural, Electrical,and Magnetic Properties of Dy2CoIrO6: A 3d–5d–4f Heterotri-Spin System Dy2CoIrO6: 3d-5d-4f异质自旋体系的结构、电学和磁性综合研究

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-15 DOI: 10.1021/acs.inorgchem.6c02800

Mithun Kumar Majee,Divya Prakash Dubey,Balwant Singh Chauhan,Ratnamala Chatterjee,Radheshyam Rai

{"title":"Comprehensive Investigation of Structural, Electrical,\u0000and Magnetic Properties of Dy2CoIrO6: A\u0000 3d–5d–4f\u0000 Heterotri-Spin System","authors":"Mithun Kumar Majee,Divya Prakash Dubey,Balwant Singh Chauhan,Ratnamala Chatterjee,Radheshyam Rai","doi":"10.1021/acs.inorgchem.6c02800","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c02800","url":null,"abstract":"Abstract In this work, we present a comprehensive investigation of the structural, electrical, and magnetic properties of Dy2CoIrO6, a 3d–5d–4f heterotri-spin system. X-ray diffraction analysis confirms a distorted monoclinic crystal structure (space group: P21/n) with slight antisite disorder (∼8%) between the Co and Ir ions. X-ray photoelectron spectroscopy reveals the coexistence of mixed valence of Co2+/3+ and Ir4+/5+ ions. The high electrical resistivity confirms the insulating nature of the compound, while the low-temperature transport behavior is well described by the 3D variable-range hopping model. The dc magnetization exhibits two magnetic transition temperatures at TN1 = 21.5 K and TN2 = 145 K, together with a magnetic compensation temperature of approximately 61 K. The magnetic transition below TN1 is attributed to weak ferrimagnetic ordering arising from antiferromagnetic coupling between the Dy(4f) and Co(3d)/Ir(5d) sublattices, whereas the transition at TN2 is associated with antiferromagnetic ordering resulting from antiferromagnetic interactions between the Co and Ir spins. A detailed analysis of the ac susceptibility exhibits a pronounced frequency dependence of the spin-freezing temperature, indicating the presence of glassy magnetic behavior below 11.5 K in Dy2CoIrO6 compound.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210107","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}

引用次数: 0