Inorganic Chemistry最新文献

{"title":"Preparation of Colloidal Cadmium Sulfoselenide Nanoplatelets from Alloyed Quantum Dots","authors":"Yan Zhang, Ye Zhu, Jianhui Jiang, Yong Chen, Zheng Li","doi":"10.1021/acs.inorgchem.4c05344","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05344","url":null,"abstract":"We report a novel approach for synthesizing cadmium sulfoselenide nanoplatelets from alloyed quantum dots. The resulting nanoplatelets, with a zinc-blende crystal structure, display uniform morphology, sharp photoluminescence, and spatially homogeneous elemental distributions. Correlated analyses corroborate the evolution of cadmium sulfoselenide nanoplatelets derived from alloyed quantum dots prepared with selenium sulfide.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"189 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758343","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}

{"title":"Unveiling the Dichotomy Between Cobalt(II)-Exchanged X and Y Faujasite Zeolites via Oxidative Carboxylation of Alkene to Cyclic Carbonate","authors":"Sakshi Bajaj, Saumi Ray","doi":"10.1021/acs.inorgchem.5c00082","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00082","url":null,"abstract":"Cobalt(II)-exchanged X and Y zeolites with varying metal loadings were employed to convert CO₂ to cyclic carbonates starting from alkenes. The transformation was carried out using O₂ as an oxidant in a mixture of O₂ and CO₂ under atmospheric pressure, and a maximum yield of 35.7% cyclic carbonate was achieved. Studies revealed a stark difference among both the zeolites, primarily arising from a difference in their ion exchange behaviors. Their catalytic and recyclability properties differed as a result of this variation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"107 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758744","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}

{"title":"Structural, Optoelectronic, Magnetic, and Photoelectrochemical Consequences of Copper Insertion into Alkaline Earth Metal (Mg, Ca, or Sr) Pyrovanadate Compound Frameworks","authors":"Abhishek Rawat, Fahad I. Danladi, Hori Pada Sarker, Chuzhong Zhang, Jacob Fulton, Riddhi Ananth, Alessandro Pereyra, Shreyash S. Hadke, Sumit Kewalramani, Vinod K. Sangwan, Peter S. Toth, Csaba Janáky, Michael J. Bedzyk, Mark C. Hersam, Efstathios I. Meletis, Krishnan Rajeshwar","doi":"10.1021/acs.inorgchem.5c00280","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00280","url":null,"abstract":"This study explores the manifold consequences of introducing copper into an alkaline earth metal (A = Mg, Ca, or Sr) pyrovanadate compound (A₂V₂O₇) framework. Thus, powder X-ray diffraction coupled with Rietveld refinement showed that phase pure alloys, namely, Mg_0.67Cu_1.33V₂O₇, CaCuV₂O₇, and SrCuV₂O₇ could be obtained via solution combustion synthesis. Local structure distortions from copper insertion into the A₂V₂O₇ compound framework were revealed by Raman spectroscopy and X-ray photoelectron spectroscopy. Importantly, the Cu_2–<i>x</i>A_<i>x</i>V₂O₇ alloy framework is shown below to be an excellent platform for demonstrating the complementarity of the two outcomes of bandgap photon absorption, namely, photovoltaic or photoelectrochemical (PEC) activity versus photoluminescence (PL). Thus, PL from the parent pyrovanadate was quenched when copper was introduced; concomitantly, PEC activity emerged for the semiconductor alloys. Changes in the electronic band structures on copper introduction were experimentally probed by diffuse reflectance spectroscopy and Kelvin probe measurements. These data were complemented by density functional theory (DFT) calculations. Finally, the magnetic attributes of the three alloys are discussed via both experiment and theory.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"37 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766932","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}

{"title":"Organotin-Oxo Clusters with Enhanced π-Conjugation for Iodine Capture","authors":"Gui-Xin Yan, Er-Xia Chen, Jin-Xia Yang, Jian Zhang, Qipu Lin","doi":"10.1021/acs.inorgchem.4c05502","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05502","url":null,"abstract":"The sustainable development of nuclear energy raises significant challenges in handling radioactive iodine (I₂). Tin-oxo clusters are multimetal aggregates composed of Sn-oxide motifs and surface ligands. Sn^2/4+ ions have a strong affinity for iodine, making tin-oxo clusters promising candidates for trapping I₂. In this work, we constructed two BINOL (=1,1′-binaphthol)-based organotin-oxo clusters with bowl-shaped structures and used them in iodine absorption study. The BINOL-based organotin-oxo clusters demonstrated remarkable performance in an I₂ vapor adsorption experiment, with Sn₆L₄ achieving an adsorption capacity of 1.36 g·g^–1 at 80 °C. Combining experimental characterizations and theoretical calculations, we found that the BINOL-based organotin-oxo clusters interact with iodine through charge transfer interactions and Sn–I bondings. Additionally, the introduction of a butyl group enhances the adsorption capacity by facilitating C–H–I interactions. The research paves the way for the development of tin-oxo cluster-based iodine adsorbents.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758349","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}

{"title":"Giant Polyoxometalate Acting as a Nanofiller into a Polymer to Fabricate Proton Exchange Membranes Exhibiting Super Proton Conductivity","authors":"Hema Kumari Kolli, Anupam Das, Debu Jana, Ritu Saraswat, Tushar Jana, Samar K. Das","doi":"10.1021/acs.inorgchem.5c00634","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00634","url":null,"abstract":"The crystalline <b>{Mo</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}</b> and <b>{W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}</b> Keplerates, a polyoxometalate (POM) system, were synthesized in Bielefeld, Germany, by Müller’s research group. Subsequently, Liu, Müller, and their co-workers demonstrated the formation of nanoblackberries of <b>{Mo</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}</b> and <b>{W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}</b> in respective aqueous solutions. In this work, we have shown that the isolated tungsten blackberries, Fe₃[W₇₂Fe₃₀O₂₅₂(CH₃COO)₂(OH)₂₅(H₂O)₁₀₃]·180H₂O (<b>{W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}</b>_<b>NB</b>) exhibit a modest proton conductivity of 3.0 × 10^–3 S cm^–1 at 80 °C and RH 98% with an activation energy of 0.34 eV. We have used this POM-based solid electrolyte of moderate proton conductivity as the nanofiller in an organic polymer, poly [2,2′-(m-phenylene)- 5, 5′-benzimidazole] (m-PBI) to fabricate the POM-based polymer composite membranes that are doped with phosphoric acid (PA): <b>2</b>.<b>5% {W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}+PA@m-PBI</b> and <b>5% {W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}+PA@m-PBI</b> for their use as proton exchange membranes (PEMs) at a higher temperature (160 °C). The PEMs, <b>2</b>.<b>5% {W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}+PA@m-PBI</b> and <b>5% {W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}+PA@m-PBI</b>, exhibit the proton conductivity values of 0.126 S cm^–1 and 0.159 S cm^–1, respectively, whereas the PA-doped host-organic polymer (<b>PA@m-PBI</b>) itself shows the conductivity value of 0.056 S cm^–1, under an identical experimental condition. Thus, we have demonstrated that a giant <b>{W</b>_<b>72</b><b>Fe</b>_<b>30</b><b>}</b>-type POM compound showing a moderate proton conductivity in its solid state exhibits super proton conductivity upon its fabrication with an organic polymer, resulting in mixed matrix PEMs.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766933","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}

{"title":"FRET-Mediated Photoswitchable Catalytic Metallacage with Tunable Activity for Organic Dye Degradation","authors":"Gui-Yuan Wu, Ling Hu, Ling Zhu, Zi-Yi Xu, Wei-Liang Hu, Lianrui Hu, Yi Qin, Xiao He, Ben Zhong Tang, Zhou Lu","doi":"10.1021/acs.inorgchem.4c05231","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05231","url":null,"abstract":"Photoswitchable catalysts provide a versatile strategy for controlling catalytic activities through light stimuli, presenting significant potential for the precise regulation of synthetic transformations. Herein, we successfully synthesized a novel photoswitchable catalytic metallacage <b>MC</b> from meso-tetra-(2-pyridyl)-porphines (<b>TPP</b>) and Pt(II)-bisthienylethene (<b>DTE-1</b>) via coordination-driven self-assembly. The Pt(II)-bisthienylethene ligand within the metallacage exhibits a reversible conversion between its ring-opened and ring-closed isomers upon alternating UV and visible radiation, facilitating photoswitchable Förster resonance energy transfer (FRET) in <b>MC</b> systems. Notably, the two forms of the metallacage exhibit switchable performance between highly and poorly catalytical activity for the degradation of Rhodamine B. This work not only develops a novel metallacage-based photoswitchable FRET system but also provides a new avenue for constructing artificial photoregulated enzymes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758338","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}

{"title":"Molecular Switches Guided by a Reversible Access to Room-Temperature Phosphorescence and ESIPT Fluorescence","authors":"Vyacheslav E. Olennikov, Valentina V. Zvereva, Vladimir V. Kriventsov, Sergey N. Konchenko, Taisiya S. Sukhikh","doi":"10.1021/acs.inorgchem.5c00222","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00222","url":null,"abstract":"This work contributes to luminescent molecular switches featuring several emission pathways, which can be activated by external stimuli. We designed Zn complexes with phenylbenzothiazole-based α-aminomethylphosphine oxide (L) and isolated them as crystalline phases, α-[ZnL₂Cl₂], [ZnL(EtOAc)Cl₂], [ZnL₂Cl₂]·1.5CH₂Cl₂, and [ZnL₂Cl₂]·1.5CHCl₃. They feature an intramolecular hydrogen bond of medium strength, capable of excited-state intramolecular proton transfer (ESIPT), as well as able for intersystem crossing between singlet and triplet states. Since neither of these processes is predominant, one or the other can occur depending on a slight change in a molecular geometry. The crystalline phases reveal red-colored ESIPT fluorescence, while a metastable amorphous phase β-[ZnL₂Cl₂] with a similar structure of the coordination center reveals yellow-colored room-temperature phosphorescence. Combined experimental and quantum-chemical TD-DFT study clarified the dual emission behavior for the polymorphs α-[ZnL₂Cl₂] and β-[ZnL₂Cl₂], which is attributed to the high dependence of the probability of the excited-state processes on the geometry of the phenylbenzothiazole moiety. The reversible phase transition, accompanied by the change in the emission mechanism (ESIPT fluorescence vs phosphorescence), can be manipulated by fuming with CHCl₃ and Et₂O, respectively. We have demonstrated good adhesive properties of the polymer-free β-[ZnL₂Cl₂] film toward glass and plastic, naked-eye color response to fuming with Et₂O, and easy recovery with CHCl₃.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"58 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766931","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}

{"title":"Zinc Sulfate Open Frameworks with Nonconventional Room-Temperature Phosphorescence for Selective Amine Vapor Detection","authors":"Lei Miao, Bo-Lun Zhang, Wen-Tao Song, Jun Chen, Wen-Jing Shi, Rui-Hong Wang, Shuqin Liu, Ying-Jia Li, Jian-Jun Zhang","doi":"10.1021/acs.inorgchem.5c00917","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00917","url":null,"abstract":"Molecular-based afterglow materials have garnered significant attention due to their diverse applications. However, most studies focus on conventional luminophores, leaving nonconventional systems underexplored, particularly regarding the screening of new material subclasses and the development of applications such as sensing. Herein we report the successful preparation of two new two-dimensional ZnSO₄-based open-framework materials (OFMs)─(H₂DABCO)[Zn₃(μ₃-OH)₂(SO₄)₃]·H₂O (<b>1</b>) and (H₂DABCO)[Zn(SO₄)₂] (<b>2</b>)─through self-assembly of Zn²⁺/SO₄^2– with nonaromatic triethylenediamine (DABCO). Both compounds exhibit distinct delayed emission characteristics with lifetimes of 259.10 ms (<b>1</b>) and 49.62 μs (<b>2</b>), respectively. Frontier orbital analysis reveals the key role of charge transfer between sulfate groups to (H₂DABCO)²⁺ cations in the luminescence. Notably, <b>1</b> demonstrates exceptional performance as an afterglow probe for the selective detection of <i>n</i>-propylamine and <i>n</i>-butylamine vapors, achieving detection limits of 32.99 and 47.18 ppm, respectively. The sensing mechanism involves a phase-transition process, and the luminescence change can be observed by the naked eye. This work pioneers the integration of sulfate-based OFMs with nonconventional room-temperature phosphorescence properties, demonstrating their potential as afterglow probes for industrial and environmental monitoring.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766935","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}

{"title":"Excellent Upconversion Luminescence Obtained by Er3+ Self-Sensitization for Temperature Sensing in Deep Tissues and Anticounterfeiting Application","authors":"Guotao Xiang, Hongdou Chen, YuanYuan Yi, Zhiyu Yang, Yongjie Wang, Lu Yao, Xianju Zhou, Li Li, Xiaojun Wang, Jiahua Zhang","doi":"10.1021/acs.inorgchem.5c00728","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00728","url":null,"abstract":"The development of high-efficiency upconversion (UC) luminescent materials with multifunctional applications, particularly those excited by wavelengths within the second near-infrared (NIR) biological window, holds a paramount scientific significance. Herein, Er³⁺ self-sensitization UC performance excited by 1532 nm wavelength is first studied in the CaSc₂O₄ matrix. Strong green and red UC emission as well as ⁴I_11/2 → ⁴I_15/2 NIR transition are observed, though multipath optical thermometry with high sensitivity is realized. Moreover, the penetration depth of the ⁴I_11/2 → ⁴I_15/2 transition in the biological tissues can reach at least 6 mm, benefiting from its ideal excitation and emission wavelengths located in the biological window. Beyond that, CaSc₂O₄: Er³⁺ phosphor displays variable color luminescence under dual-wavelength excitation, including 980 and 1532 nm, which can be used for enhancing the security of anticounterfeiting materials. Our findings suggest that CaSc₂O₄: Er³⁺ phosphor with excellent UC properties is a promising candidate for the application in optical thermometry and anticounterfeiting field.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"73 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766934","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}

{"title":"Enlarging Environmental Asymmetry by the Site Tailoring to Enhance Luminescence Properties of Sm3+ in the (Gd,Na)3(Ga,In)2(Ga,Ge)3O12 Garnet","authors":"Jiajun Feng, Yongxin Yu, Hongji Song, Zibo Chen, Yingxiang Zhu, Jiahui Liu, Jingtian Xie, Lianfen Chen, Junhao Li","doi":"10.1021/acs.inorgchem.5c00549","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00549","url":null,"abstract":"A structural design strategy was employed to develop NaGd₂Ga₂InGe₂O₁₂:Sm³⁺ (NGGIG:Sm³⁺) garnet phosphors, optimizing the local coordination environment to enhance luminescence performance. By tailoring site occupation, Sm³⁺ ions were incorporated into an asymmetric crystal field, where a statistical probability model confirmed that ∼97% of Sm³⁺ ions reside in distorted coordination environments, promoting electric dipole(ED) transitions. The phosphors exhibit a high red-to-orange (<i>R</i>/<i>O</i>) intensity ratio of 2.97, contributing to enhanced red emission. CIE chromaticity coordinates of (0.61, 0.39) indicate a significant shift toward the red region, and the phosphors retain over 70% of their luminescence intensity at 400 K, demonstrating good thermal stability. These characteristics make NGGIG:Sm³⁺ a promising candidate for high-performance red phosphors in solid-state lighting applications, highlighting the effectiveness of site engineering in garnet structures for optimizing luminescence efficiency and stability.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758344","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}