Pub Date : 2026-03-18DOI: 10.1021/acs.inorgchem.6c00258
Jun Zheng, Jiawei Cheng, Ying Wang, Yaping Gong, Yunwu Li, Guang-Ning Liu, Suna Wang
A highly stable heterometallic metal–organic framework (MOF), {[KCd(HL)]·DMF} (H4L = 2,5-di(2“,4”-dicarboxyphenyl)-1,4-difluoro-benzene), denoted as LCU-118 (LCU = Liaocheng University), was successfully synthesized via a solvothermal approach. Aqueous suspensions of LCU-118 exhibit remarkable photoluminescent discoloration upon continuous ultraviolet (UV) irradiation. Moreover, LCU-118 demonstrates the efficient detection of nitrofurantoin (NFT) and nitrofurazone (NZF) through a fluorescence quenching mechanism. Interestingly, the fluorescence quenched by NFT can be recovered to some extent after UV irradiation, which provides a reliable method for distinguishing NFT from NZF. Additionally, LCU-118 displays excellent catalytic activity toward the oxidation of methyl phenyl sulfide (MPS) at room temperature, offering a novel strategy for the efficient utilization of green energy. Mechanistic investigations reveal that the generation of superoxide radicals in the suspensions is involved in endowing LCU-118 with such multifunctional properties..
{"title":"Photochromic Heterometallic Metal–Organic Framework as a Multifunctional Platform for Antibiotic Sensing and Sulfide Photooxidation","authors":"Jun Zheng, Jiawei Cheng, Ying Wang, Yaping Gong, Yunwu Li, Guang-Ning Liu, Suna Wang","doi":"10.1021/acs.inorgchem.6c00258","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00258","url":null,"abstract":"A highly stable heterometallic metal–organic framework (MOF), {[KCd(HL)]·DMF} (H<sub>4</sub>L = 2,5-di(2“,4”-dicarboxyphenyl)-1,4-difluoro-benzene), denoted as <b>LCU-118</b> (LCU = Liaocheng University), was successfully synthesized via a solvothermal approach. Aqueous suspensions of <b>LCU-118</b> exhibit remarkable photoluminescent discoloration upon continuous ultraviolet (UV) irradiation. Moreover, <b>LCU-118</b> demonstrates the efficient detection of nitrofurantoin (NFT) and nitrofurazone (NZF) through a fluorescence quenching mechanism. Interestingly, the fluorescence quenched by NFT can be recovered to some extent after UV irradiation, which provides a reliable method for distinguishing NFT from NZF. Additionally, <b>LCU-118</b> displays excellent catalytic activity toward the oxidation of methyl phenyl sulfide (MPS) at room temperature, offering a novel strategy for the efficient utilization of green energy. Mechanistic investigations reveal that the generation of superoxide radicals in the suspensions is involved in endowing <b>LCU-118</b> with such multifunctional properties..","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"236 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478618","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 : 2026-03-18DOI: 10.1021/acs.inorgchem.6c00267
Jia Ma, Xiao-Hui Li, Xin-Xin Zhang, Xiu-Li Wang
The epoxidation reaction of olefins represents a critically important oxidative process in industrial and synthetic chemistry. The development of novel heterogeneous catalysts for efficiently catalyzing olefin epoxidation is of great practical significance. In this study, three new isostructural polyoxometalate-based metal–organic complexes (POMOCs), H[Co(bpyb)2(PMo12O40)(H2O)2]·H2O (Co-PMo12), H[Co(bpyb)2(PW12O40)(H2O)2]·H2O (Co-PW12), and H[Zn(bpyb)2(PMo12O40)(H2O)2] (Zn-PMo12), were synthesized by reacting CoII or ZnII as the metal centers with H3PMo12O40 or H3PW12O40 and the ligand N,N′-bis(4-pyrimidinecarboxaido)-1,4-butane (bpyb). The three POMOCs were characterized by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy. In the epoxidation reaction of cis-cyclooctene, both Co-POMOCs exhibited high catalytic efficiency. Under an O2 atmosphere at 55 °C, they achieved 98% conversion of cis-cyclooctene within 10 min (Co-PMo12) and 14 min (Co-PW12), respectively, with 100% selectivity for 1,2-epoxycyclooctane in both cases. A synergistic catalysis between the CoII and POM sites in Co-PMo12 for the epoxidation of olefins was confirmed through the catalytic activity comparison with those of its components and Zn-PMo12.
烯烃的环氧化反应是工业化学和合成化学中一个非常重要的氧化过程。开发新型非均相催化剂高效催化烯烃环氧化具有重要的现实意义。本研究以CoII或ni为金属中心，与H3PMo12O40或H3PW12O40及配体N，N′-双（4-嘧啶羧基）-1,4-丁烷（bpyb）反应，合成了三种新型同构多金属氧酸盐基金属有机配合物（POMOCs）， H[Co(bpyb)2(PMo12O40)(H2O)2]·H2O (Co- pmo12), H[Co(bpyb)2(PW12O40)(H2O)2]·H2O (Co- pw12), H[Zn(bpyb)2(PMo12O40)(H2O)2] （Zn- pmo12）。采用单晶x射线衍射、傅里叶变换红外光谱、粉末x射线衍射和x射线光电子能谱对三种POMOCs进行了表征。在顺式环烯的环氧化反应中，两种Co-POMOCs均表现出较高的催化效率。在55°C的O2气氛下，它们分别在10 min （Co-PMo12）和14 min （Co-PW12）内实现了98%的顺式环辛烯转化率，在这两种情况下，1,2-环氧环辛烷的选择性均为100%。通过与其组分和Zn-PMo12的催化活性比较，证实了Co-PMo12中CoII和POM位点对烯烃环氧化反应具有协同催化作用。
{"title":"Dual-Site Polyoxometalate-Based Cobalt Complexes for Catalytic Epoxidation Reaction of Olefins","authors":"Jia Ma, Xiao-Hui Li, Xin-Xin Zhang, Xiu-Li Wang","doi":"10.1021/acs.inorgchem.6c00267","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00267","url":null,"abstract":"The epoxidation reaction of olefins represents a critically important oxidative process in industrial and synthetic chemistry. The development of novel heterogeneous catalysts for efficiently catalyzing olefin epoxidation is of great practical significance. In this study, three new isostructural polyoxometalate-based metal–organic complexes (POMOCs), H[Co(bpyb)<sub>2</sub>(PMo<sub>12</sub>O<sub>40</sub>)(H<sub>2</sub>O)<sub>2</sub>]·H<sub>2</sub>O (<b>Co-PMo</b><sub><b>12</b></sub>), H[Co(bpyb)<sub>2</sub>(PW<sub>12</sub>O<sub>40</sub>)(H<sub>2</sub>O)<sub>2</sub>]·H<sub>2</sub>O (<b>Co-PW</b><sub><b>12</b></sub>), and H[Zn(bpyb)<sub>2</sub>(PMo<sub>12</sub>O<sub>40</sub>)(H<sub>2</sub>O)<sub>2</sub>] (<b>Zn-PMo</b><sub><b>12</b></sub>), were synthesized by reacting Co<sup>II</sup> or Zn<sup>II</sup> as the metal centers with H<sub>3</sub>PMo<sub>12</sub>O<sub>40</sub> or H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> and the ligand <i>N,N′</i>-bis(4-pyrimidinecarboxaido)-1,4-butane (bpyb). The three POMOCs were characterized by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy. In the epoxidation reaction of <i>cis</i>-cyclooctene, both Co-POMOCs exhibited high catalytic efficiency. Under an O<sub>2</sub> atmosphere at 55 °C, they achieved 98% conversion of <i>cis</i>-cyclooctene within 10 min (<b>Co-PMo</b><sub><b>12</b></sub>) and 14 min (<b>Co-PW</b><sub><b>12</b></sub>), respectively, with 100% selectivity for 1,2-epoxycyclooctane in both cases. A synergistic catalysis between the Co<sup>II</sup> and POM sites in <b>Co-PMo</b><sub><b>12</b></sub> for the epoxidation of olefins was confirmed through the catalytic activity comparison with those of its components and <b>Zn-PMo</b><sub><b>12</b></sub>.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478619","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 : 2026-03-18DOI: 10.1021/acs.inorgchem.6c00868
Xiaoman Li,Yiming Wang,Xue Yang,Chaojin Jiang,Lulu Kong,Honghan Fei,Xueling Song
Organolead halide coordination polymers have emerged as promising photocatalysts owing to their attractive photophysical properties and structural tunability. However, organolead bromides typically exhibit limited photocatalytic performance due to their generally narrow light absorption range and inefficient carrier mobility. To overcome these issues, we designed and synthesized a robust layered organolead bromide coordination polymer templated by the squaric acid ligand featuring short carbon chains and broad near-UV absorption. It achieves visible light absorption and high charge separation efficiency, in contrast to the two reported lead bromide analogues with large interlayer spacing. Upon exposure to AM 1.5G simulated sunlight, the hybrid bromoplumbate exhibits enhanced photocatalytic activity for CO2-CO conversion, with high product selectivity and cycling stability. Moreover, the photocatalytic CO2 reduction performance is further promoted by in situ incorporation of trace Ag nanocrystals as reductive cocatalysts for suppressing carrier recombination, prolonging charge lifetime, and reducing free energy for the *COOH key intermediate. This work underscores the critical role of coordination chemistry in modulating the relationship between the structure and property of crystalline materials.
{"title":"Squaric Acid Templated an Organolead Bromide Coordination Polymer with Visible Light Response for Photocatalytic CO2 Reduction.","authors":"Xiaoman Li,Yiming Wang,Xue Yang,Chaojin Jiang,Lulu Kong,Honghan Fei,Xueling Song","doi":"10.1021/acs.inorgchem.6c00868","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00868","url":null,"abstract":"Organolead halide coordination polymers have emerged as promising photocatalysts owing to their attractive photophysical properties and structural tunability. However, organolead bromides typically exhibit limited photocatalytic performance due to their generally narrow light absorption range and inefficient carrier mobility. To overcome these issues, we designed and synthesized a robust layered organolead bromide coordination polymer templated by the squaric acid ligand featuring short carbon chains and broad near-UV absorption. It achieves visible light absorption and high charge separation efficiency, in contrast to the two reported lead bromide analogues with large interlayer spacing. Upon exposure to AM 1.5G simulated sunlight, the hybrid bromoplumbate exhibits enhanced photocatalytic activity for CO2-CO conversion, with high product selectivity and cycling stability. Moreover, the photocatalytic CO2 reduction performance is further promoted by in situ incorporation of trace Ag nanocrystals as reductive cocatalysts for suppressing carrier recombination, prolonging charge lifetime, and reducing free energy for the *COOH key intermediate. This work underscores the critical role of coordination chemistry in modulating the relationship between the structure and property of crystalline materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471702","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 conversion of CO2/H2O into valuable chemicals with nonthermal plasma (NTP) under mild conditions represents a promising strategy, whereas the quenching effect and side reactions caused by H2O seriously restrict its efficiency. Herein, we propose a surface microenvironment modulation strategy by confining phosphomolybdic acid (PMA) within UiO-66 to construct a highly hydrophilic PMA/UiO-66 catalyst for plasma-catalytic CO2 conversion in a dielectric barrier discharge system. Theoretical calculations and experimental results confirm that the abundant exposed oxygen atoms in PMA/UiO-66 can form a hydrogen-bonding network with H2O molecule, which effectively promotes the enrichment and activation of H2O on the catalyst surface and suppresses the quenching effect of bulk H2O molecules on the plasma-induced dissociation of CO2. Meanwhile, the hydrogen-bonding network acts as an electron-trapping center and proton transport channel, lowering the free energy barrier for CO2-to-*COOH step, thereby accelerating the reaction kinetics of CO2 conversion. Under optimal energy efficiency conditions for NTP-catalyzed CO2 conversion, the PMA/UiO-66 system achieves a CO2 conversion of 17.78%, which is approximately 5 times greater than that of the plasma-only system. The study on the regulation of the catalyst surface microenvironment offers valuable insights for designing high-performance catalysts for plasma-catalytic CO2 conversion.
{"title":"Synergistic Enhancement of CO2 Conversion via Surface Microenvironment Engineering in a Nonthermal Plasma.","authors":"Hongxiang Jin,Xiaochuan Deng,Rong He,Lingyu Xie,Xue Wang,Han Yan,Aiping Zhang,Xiaofang Feng,Tao Chen,Wenkun Zhu","doi":"10.1021/acs.inorgchem.5c05818","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05818","url":null,"abstract":"The conversion of CO2/H2O into valuable chemicals with nonthermal plasma (NTP) under mild conditions represents a promising strategy, whereas the quenching effect and side reactions caused by H2O seriously restrict its efficiency. Herein, we propose a surface microenvironment modulation strategy by confining phosphomolybdic acid (PMA) within UiO-66 to construct a highly hydrophilic PMA/UiO-66 catalyst for plasma-catalytic CO2 conversion in a dielectric barrier discharge system. Theoretical calculations and experimental results confirm that the abundant exposed oxygen atoms in PMA/UiO-66 can form a hydrogen-bonding network with H2O molecule, which effectively promotes the enrichment and activation of H2O on the catalyst surface and suppresses the quenching effect of bulk H2O molecules on the plasma-induced dissociation of CO2. Meanwhile, the hydrogen-bonding network acts as an electron-trapping center and proton transport channel, lowering the free energy barrier for CO2-to-*COOH step, thereby accelerating the reaction kinetics of CO2 conversion. Under optimal energy efficiency conditions for NTP-catalyzed CO2 conversion, the PMA/UiO-66 system achieves a CO2 conversion of 17.78%, which is approximately 5 times greater than that of the plasma-only system. The study on the regulation of the catalyst surface microenvironment offers valuable insights for designing high-performance catalysts for plasma-catalytic CO2 conversion.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471706","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 : 2026-03-18DOI: 10.1021/acs.inorgchem.5c05877
Hang Yu,Guodong Sun,Huijuan Deng,Lin Xiong,Shan Jin,Manzhou Zhu
Copper-based nanoclusters are promising electrocatalysts for CO2 reduction (eCO2RR), where the surface structure and electronic properties critically determine performance. The introduction of the PPh2Py-CH3 ligand effectively tailors the Cu8 surface, modulating its electronic configuration and optimizing the eCO2RR activity. Coprotection with PPh2Py and PPh2Py-CH3 enables the synthesis of the two-electron cluster [Cu8H4(PPh2Py)2(PPh2Py-CH3)4]2+. Compared with the isostructural zero-electron [Cu8H6(PPh2Py)6]2+ and [Cu8H6(PPh3)2(PPh2Py-CH3)4]2+ analogues, the two-electron form exhibits concurrent geometric and electronic modulation, along with fewer hydrides. Electrochemical measurements reveal that [Cu8H4(PPh2Py)2(PPh2Py-CH3)4]2+ achieves the highest CO Faradaic efficiency (80.0% at -1.0 V vs RHE), outperforming the other clusters. Density functional theory calculations attribute this enhancement to the low atomic dipole-corrected Hirshfeld atomic charge (ADCH) and partial Cu(0) character of the active site, which facilitates CO2 adsorption and lowers the *COOH formation barrier. This work demonstrates that ligand-induced surface reconstruction is an effective approach to tune Cu cluster catalysts for the high-performance eCO2RR.
铜基纳米团簇是很有前途的二氧化碳还原（eCO2RR）电催化剂，其表面结构和电子性质决定了其性能。PPh2Py-CH3配体的引入有效地调整了Cu8表面，调节了其电子构型并优化了eCO2RR活性。与PPh2Py和PPh2Py- ch3共保护可合成双电子簇[Cu8H4(PPh2Py)2(PPh2Py- ch3)4]2+。与同结构的零电子[Cu8H6(PPh2Py)6]2+和[Cu8H6(PPh3)2(PPh2Py- ch3)4]2+类似物相比，双电子形式表现出同步的几何和电子调制，并且氢化物较少。电化学测量结果表明，[Cu8H4(PPh2Py)2(PPh2Py- ch3)4]2+在-1.0 V vs RHE下具有最高的CO法拉第效率（80.0%），优于其他簇。密度泛函理论计算将这种增强归因于低原子偶极修正的Hirshfeld原子电荷（ADCH）和活性位点的部分Cu(0)特征，这有利于CO2吸附和降低*COOH形成势垒。这项工作表明，配体诱导的表面重建是一种有效的方法来调整Cu簇催化剂的高性能eCO2RR。
{"title":"Dual-Ligand Engineering Induces Partial Cu(0) Character in a 2-Electron [Cu8H4(PPh2Py)2(PPh2Py-CH3)4]2+ Cluster for Enhanced CO2 Electroreduction.","authors":"Hang Yu,Guodong Sun,Huijuan Deng,Lin Xiong,Shan Jin,Manzhou Zhu","doi":"10.1021/acs.inorgchem.5c05877","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05877","url":null,"abstract":"Copper-based nanoclusters are promising electrocatalysts for CO2 reduction (eCO2RR), where the surface structure and electronic properties critically determine performance. The introduction of the PPh2Py-CH3 ligand effectively tailors the Cu8 surface, modulating its electronic configuration and optimizing the eCO2RR activity. Coprotection with PPh2Py and PPh2Py-CH3 enables the synthesis of the two-electron cluster [Cu8H4(PPh2Py)2(PPh2Py-CH3)4]2+. Compared with the isostructural zero-electron [Cu8H6(PPh2Py)6]2+ and [Cu8H6(PPh3)2(PPh2Py-CH3)4]2+ analogues, the two-electron form exhibits concurrent geometric and electronic modulation, along with fewer hydrides. Electrochemical measurements reveal that [Cu8H4(PPh2Py)2(PPh2Py-CH3)4]2+ achieves the highest CO Faradaic efficiency (80.0% at -1.0 V vs RHE), outperforming the other clusters. Density functional theory calculations attribute this enhancement to the low atomic dipole-corrected Hirshfeld atomic charge (ADCH) and partial Cu(0) character of the active site, which facilitates CO2 adsorption and lowers the *COOH formation barrier. This work demonstrates that ligand-induced surface reconstruction is an effective approach to tune Cu cluster catalysts for the high-performance eCO2RR.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147471710","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 solid solution Rh1–xPtxSb, bridging the structurally distinct MnP-type RhSb and NiAs-type PtSb, was systematically investigated. A temperature-induced structural phase transition between the MnP- and NiAs-type phases occurs at x ≈ 0.1 near room temperature, accompanied by pronounced resistivity hysteresis. Superconductivity emerges for x ≥ 0.2, and the critical temperature (Tc) reaches a maximum value of 4.25 K at x = 0.4─the highest Tc among transition-metal monoantimonides. The electron–phonon coupling constant (λep ≈ 0.6) and normalized specific-heat jump (ΔCel/γTc ≈ 1.6) classify Rh1–xPtxSb as a weak-coupling superconductor. The compositional dependence of both the Debye temperature (ΘD) and the electronic density of states at the Fermi level (N(EF)) correlates closely with Tc, suggesting that they are responsible for the Tc enhancement. A comparison with the high-entropy analogue M1–xPtxSb (M = equimolar Ru, Rh, Pd, and Ir) revealed distinct differences in ΘD and N(EF), which can account for the observed difference in Tc between the two systems.
{"title":"Enhanced Superconductivity and Structural Phase Transition in the Solid Solution Rh1–xPtxSb","authors":"Akira Iyo, Hiroshi Fujihisa, Izumi Hase, Shigeyuki Ishida, Hiroshi Eisaki, Hiraku Ogino, Kenji Kawashima","doi":"10.1021/acs.inorgchem.5c05744","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05744","url":null,"abstract":"The solid solution Rh<sub>1–<i>x</i></sub>Pt<sub><i>x</i></sub>Sb, bridging the structurally distinct MnP-type RhSb and NiAs-type PtSb, was systematically investigated. A temperature-induced structural phase transition between the MnP- and NiAs-type phases occurs at <i>x</i> ≈ 0.1 near room temperature, accompanied by pronounced resistivity hysteresis. Superconductivity emerges for <i>x</i> ≥ 0.2, and the critical temperature (<i>T</i><sub>c</sub>) reaches a maximum value of 4.25 K at <i>x</i> = 0.4─the highest <i>T</i><sub>c</sub> among transition-metal monoantimonides. The electron–phonon coupling constant (<i>λ</i><sub>ep</sub> ≈ 0.6) and normalized specific-heat jump (Δ<i>C</i><sub>el</sub>/<i>γ</i><i>T</i><sub>c</sub> ≈ 1.6) classify Rh<sub>1–<i>x</i></sub>Pt<sub><i>x</i></sub>Sb as a weak-coupling superconductor. The compositional dependence of both the Debye temperature (Θ<sub>D</sub>) and the electronic density of states at the Fermi level (<i>N</i>(<i>E</i><sub>F</sub>)) correlates closely with <i>T</i><sub>c</sub>, suggesting that they are responsible for the <i>T</i><sub>c</sub> enhancement. A comparison with the high-entropy analogue <i>M</i><sub>1–<i>x</i></sub>Pt<sub><i>x</i></sub>Sb (<i>M</i> = equimolar Ru, Rh, Pd, and Ir) revealed distinct differences in Θ<sub>D</sub> and <i>N</i>(<i>E</i><sub>F</sub>), which can account for the observed difference in <i>T</i><sub>c</sub> between the two systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147478156","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 : 2026-03-17DOI: 10.1021/acs.inorgchem.5c05976
Yan Lou,Wei Jin,Ling Chen,Qunyan Wu,Naixin Zhang,Zhiwei Huang,Bowen Hu,Wangsuo Wu,Kongqiu Hu,Liyong Yuan,Weiqun Shi,Lei Mei
Uranyl (UO22+) compounds are valued for their unique ligand-to-metal charge transfer (LMCT) states, yet electron transfer (ET) mechanisms within actinide-supramolecular hybrids remain poorly understood. In this study, three photochromic uranyl compounds of cucurbit[8]uril-viologen [3]pseudorotaxane were synthesized from a supramolecular [3]pseudorotaxane ligand and uranyl cations, where two auxiliary electron-rich aromatic dicarboxylic acids, terephthalic acid (H2TA) and phthalic acid (H2PA), were also introduced to modulate the coordination environments of the uranyl center and photoinduced electron transfer process. As expected, varying types of radicals are observed in these uranyl compounds, and notably, a special kind of heterobiradical species, i.e., both O-centered radicals and N-centered radicals, emerges in the presence of the auxiliary dicarboxylic acids. A combination of in situ EPR spectroscopy and density functional theory (DFT) calculations reveals that the electron-donating ability of the carboxylate ligand determines the phototriggered electron transfer pathway from the carboxylate group to the uranyl center, thus leading to different photoresponsive behavior of the cucurbit[8]uril-viologen [3]pseudorotaxane moiety and contributing to the formation of these rare heterobiradical species. This work enhances an insightful understanding of electron transfer behavior of photoresponsive actinide-organic hybrid materials, and more importantly, provides a feasible way to tune solid-state uranyl photochemistry through single-crystal-to-single-crystal ligand engineering.
{"title":"Photoinduced Formation of Heterobiradical Species in Crystalline Uranyl-Organic Frameworks Incorporating Cucurbit[8]uril-Viologen [3]Pseudorotaxane.","authors":"Yan Lou,Wei Jin,Ling Chen,Qunyan Wu,Naixin Zhang,Zhiwei Huang,Bowen Hu,Wangsuo Wu,Kongqiu Hu,Liyong Yuan,Weiqun Shi,Lei Mei","doi":"10.1021/acs.inorgchem.5c05976","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05976","url":null,"abstract":"Uranyl (UO22+) compounds are valued for their unique ligand-to-metal charge transfer (LMCT) states, yet electron transfer (ET) mechanisms within actinide-supramolecular hybrids remain poorly understood. In this study, three photochromic uranyl compounds of cucurbit[8]uril-viologen [3]pseudorotaxane were synthesized from a supramolecular [3]pseudorotaxane ligand and uranyl cations, where two auxiliary electron-rich aromatic dicarboxylic acids, terephthalic acid (H2TA) and phthalic acid (H2PA), were also introduced to modulate the coordination environments of the uranyl center and photoinduced electron transfer process. As expected, varying types of radicals are observed in these uranyl compounds, and notably, a special kind of heterobiradical species, i.e., both O-centered radicals and N-centered radicals, emerges in the presence of the auxiliary dicarboxylic acids. A combination of in situ EPR spectroscopy and density functional theory (DFT) calculations reveals that the electron-donating ability of the carboxylate ligand determines the phototriggered electron transfer pathway from the carboxylate group to the uranyl center, thus leading to different photoresponsive behavior of the cucurbit[8]uril-viologen [3]pseudorotaxane moiety and contributing to the formation of these rare heterobiradical species. This work enhances an insightful understanding of electron transfer behavior of photoresponsive actinide-organic hybrid materials, and more importantly, provides a feasible way to tune solid-state uranyl photochemistry through single-crystal-to-single-crystal ligand engineering.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"27 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464795","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 : 2026-03-17DOI: 10.1021/acs.inorgchem.5c05532
Tahereh Azizivahed, Jingyan Liu, Yining Huang
This study investigates the molecular-level-induced-fit adsorption of acetylene (C2H2) and carbon dioxide (CO2) in sql-SIFSIX-bpe-Zn, a flexible, anion-pillared ultramicroporous metal–organic framework (MOF). Sql-SIFSIX-bpe-Zn undergoes distinct pressure-dependent phase transitions, enabling a high selectivity for C2H2 over CO2 and ethylene (C2H4). However, the unclear thermodynamic and kinetic mechanisms underlying this behavior, as well as limitations in models derived from single-crystal X-ray diffraction (SCXRD), necessitate further investigation. Using in situ multinuclear solid-state NMR (SSNMR) spectroscopy with isotopically enriched C2D2 and 13CO2, we directly probed gas adsorption, framework dynamics, and competitive uptake in sql-SIFSIX-bpe-Zn across 153–298 K. Variable-temperature 2H SSNMR revealed a C2D2-induced pore opening between 253 and 233 K, marking a cooperative structural transformation process that maximizes acetylene adsorption. Complementary 13C and 19F SSNMR spectra show that both the SiF62– pillars and bpe linkers participate in host–guest interactions through C–D···F hydrogen bonding and linker reorientation, while CO2 remains bound near the linker region. In mixed-gas systems, CO2 assists pore activation, but acetylene dominates adsorption, confirming its stronger affinity and selective uptake. These results provide a molecular-level mechanism for induced-fit adsorption and competitive selectivity in flexible hybrid ultramicroporous materials, guiding the design of next-generation adaptive MOF sorbents.
{"title":"Probing Induced-Fit Acetylene Adsorption and Separation in a Flexible Ultramicroporous Framework by Multinuclear SSNMR Spectroscopy: Insights Beyond Crystallography","authors":"Tahereh Azizivahed, Jingyan Liu, Yining Huang","doi":"10.1021/acs.inorgchem.5c05532","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c05532","url":null,"abstract":"This study investigates the molecular-level-induced-fit adsorption of acetylene (C<sub>2</sub>H<sub>2</sub>) and carbon dioxide (CO<sub>2</sub>) in sql-SIFSIX-bpe-Zn, a flexible, anion-pillared ultramicroporous metal–organic framework (MOF). Sql-SIFSIX-bpe-Zn undergoes distinct pressure-dependent phase transitions, enabling a high selectivity for C<sub>2</sub>H<sub>2</sub> over CO<sub>2</sub> and ethylene (C<sub>2</sub>H<sub>4</sub>). However, the unclear thermodynamic and kinetic mechanisms underlying this behavior, as well as limitations in models derived from single-crystal X-ray diffraction (SCXRD), necessitate further investigation. Using in situ multinuclear solid-state NMR (SSNMR) spectroscopy with isotopically enriched C<sub>2</sub>D<sub>2</sub> and <sup>13</sup>CO<sub>2</sub>, we directly probed gas adsorption, framework dynamics, and competitive uptake in sql-SIFSIX-bpe-Zn across 153–298 K. Variable-temperature <sup>2</sup>H SSNMR revealed a C<sub>2</sub>D<sub>2</sub>-induced pore opening between 253 and 233 K, marking a cooperative structural transformation process that maximizes acetylene adsorption. Complementary <sup>13</sup>C and <sup>19</sup>F SSNMR spectra show that both the SiF<sub>6</sub><sup>2–</sup> pillars and bpe linkers participate in host–guest interactions through C–D···F hydrogen bonding and linker reorientation, while CO<sub>2</sub> remains bound near the linker region. In mixed-gas systems, CO<sub>2</sub> assists pore activation, but acetylene dominates adsorption, confirming its stronger affinity and selective uptake. These results provide a molecular-level mechanism for induced-fit adsorption and competitive selectivity in flexible hybrid ultramicroporous materials, guiding the design of next-generation adaptive MOF sorbents.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"57 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466151","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 : 2026-03-17DOI: 10.1021/acs.inorgchem.6c00216
Daniel Fernández-Pavón,Andrés de Blas,María Martínez-Cabanas,José L Barriada,Brian O Patrick,Chris Orvig,François Bénard,Hua Yang,Luke Wharton,María de Guadalupe Jaraquemada-Peláez,Teresa Rodríguez-Blas
As an alternative to macrocyclic chelators, a family of high-denticity, acyclic chelating agents based on picolinate arms has been devised with the aim of finding versatile chelating agents for 225Ac, 161Tb, and 177Lu. This family comprises six symmetrical four-arm decadentate chelators that differ in the nature of the backbone spacer, ethylene (H4tpaen), o-phenylene (H4tpaopd), 2,3-naphtylene (H4tpaond), m-xylylene (H4tpamxd), p-xylylene (H4tpapxd), and 2-hydroxypropylene (H4tpadapo), and two dissymmetrical octadentate ligands, H3tripaen and H4asyoctapa, structurally derived from H4tpaen by the loss of one arm (the first) and the replacement of two vicinal picolinate pendent arms by acetate groups (the second). The coordination chemistry of each chelating ligand with nonradioactive Lu3+, Tb3+, and La3+ (the latter as a surrogate for [225Ac]Ac3+) has been explored to rationalize the findings in radiolabeling and human serum stability studies. With an RCY of 96% at 10-7 M, which is directly comparable to the gold standard macrocyclic chelators H2macropa and H4crown, H4tpaond is an excellent candidate for the development of radiopharmaceuticals based on 225Ac. In addition, both H4tpaen and H4tpaopd are also an opportunity for the 225Ac/155Tb theranostic pair. Meanwhile, H4asyoctapa appears to be a great opportunity, not only for developing terbium radiopharmaceuticals, but also for the promising 177Lu/155Tb pair.
{"title":"Challenging the Macrocycle Paradigm: Four-Arm, High-Denticity Acyclic Chelators for Radiopharmaceuticals Incorporating Actinium and Lanthanides.","authors":"Daniel Fernández-Pavón,Andrés de Blas,María Martínez-Cabanas,José L Barriada,Brian O Patrick,Chris Orvig,François Bénard,Hua Yang,Luke Wharton,María de Guadalupe Jaraquemada-Peláez,Teresa Rodríguez-Blas","doi":"10.1021/acs.inorgchem.6c00216","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00216","url":null,"abstract":"As an alternative to macrocyclic chelators, a family of high-denticity, acyclic chelating agents based on picolinate arms has been devised with the aim of finding versatile chelating agents for 225Ac, 161Tb, and 177Lu. This family comprises six symmetrical four-arm decadentate chelators that differ in the nature of the backbone spacer, ethylene (H4tpaen), o-phenylene (H4tpaopd), 2,3-naphtylene (H4tpaond), m-xylylene (H4tpamxd), p-xylylene (H4tpapxd), and 2-hydroxypropylene (H4tpadapo), and two dissymmetrical octadentate ligands, H3tripaen and H4asyoctapa, structurally derived from H4tpaen by the loss of one arm (the first) and the replacement of two vicinal picolinate pendent arms by acetate groups (the second). The coordination chemistry of each chelating ligand with nonradioactive Lu3+, Tb3+, and La3+ (the latter as a surrogate for [225Ac]Ac3+) has been explored to rationalize the findings in radiolabeling and human serum stability studies. With an RCY of 96% at 10-7 M, which is directly comparable to the gold standard macrocyclic chelators H2macropa and H4crown, H4tpaond is an excellent candidate for the development of radiopharmaceuticals based on 225Ac. In addition, both H4tpaen and H4tpaopd are also an opportunity for the 225Ac/155Tb theranostic pair. Meanwhile, H4asyoctapa appears to be a great opportunity, not only for developing terbium radiopharmaceuticals, but also for the promising 177Lu/155Tb pair.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147464793","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 : 2026-03-17DOI: 10.1021/acs.inorgchem.6c00107
Remya Lohithakshamenon, Kavanal P. Prasanthkumar, Hadiya Mecheri Abdulla, Pookkottu K. Sajith
Diaryliodonium salts are versatile hypervalent iodine(III) compounds whose utility as Lewis acid catalysts relies on the tunable electrophilicity of the iodine center. To enable the rational design of these catalysts, a predictive and computationally accessible electronic descriptor is essential. This study introduces the electrostatic potential at the iodine nucleus (VI) as a robust, quantitative metric to evaluate the Lewis acidity across diverse acyclic and cyclic diaryliodonium architectures. Computed VI values of diaryliodonium ions correlate strongly with established experimental benchmarks, including Gutmann–Beckett 31P NMR chemical shifts and a previously reported experimental acidity scale. Systematic analysis reveals that VI sensitively captures electronic perturbations from the substituents and ring strain. A multiple linear regression model incorporating VI and the C–I–C bond angle (Φ) successfully predicts Lewis acidity parameters for both acyclic and cyclic diaryliodonium ions on a single unified scale. This work establishes VI as a fundamental and convenient parameter for assessing Lewis acidity, providing a clear electronic design principle for developing next-generation hypervalent iodine-based catalysts.
{"title":"Electrostatic Potential at the Iodine Nucleus as a Predictive Descriptor for Lewis Acidity in Diaryliodonium Ions","authors":"Remya Lohithakshamenon, Kavanal P. Prasanthkumar, Hadiya Mecheri Abdulla, Pookkottu K. Sajith","doi":"10.1021/acs.inorgchem.6c00107","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c00107","url":null,"abstract":"Diaryliodonium salts are versatile hypervalent iodine(III) compounds whose utility as Lewis acid catalysts relies on the tunable electrophilicity of the iodine center. To enable the rational design of these catalysts, a predictive and computationally accessible electronic descriptor is essential. This study introduces the electrostatic potential at the iodine nucleus (<i>V</i><sub>I</sub>) as a robust, quantitative metric to evaluate the Lewis acidity across diverse acyclic and cyclic diaryliodonium architectures. Computed <i>V</i><sub>I</sub> values of diaryliodonium ions correlate strongly with established experimental benchmarks, including Gutmann–Beckett <sup>31</sup>P NMR chemical shifts and a previously reported experimental acidity scale. Systematic analysis reveals that <i>V</i><sub>I</sub> sensitively captures electronic perturbations from the substituents and ring strain. A multiple linear regression model incorporating <i>V</i><sub>I</sub> and the C–I–C bond angle (Φ) successfully predicts Lewis acidity parameters for both acyclic and cyclic diaryliodonium ions on a single unified scale. This work establishes <i>V</i><sub>I</sub> as a fundamental and convenient parameter for assessing Lewis acidity, providing a clear electronic design principle for developing next-generation hypervalent iodine-based catalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"94 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147466154","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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