Inorganic Chemistry最新文献_第4页

Superatomic Stabilization of Dinuclear Platinum(III) through Iodide-Bridged Five-Center Ten-Electron Bonding

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04178

Masanori Wakizaka, Hisaaki Tanaka, Shinya Takaishi, Masahiro Yamashita

{"title":"Superatomic Stabilization of Dinuclear Platinum(III) through Iodide-Bridged Five-Center Ten-Electron Bonding","authors":"Masanori Wakizaka, Hisaaki Tanaka, Shinya Takaishi, Masahiro Yamashita","doi":"10.1021/acs.inorgchem.4c04178","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04178","url":null,"abstract":"One of the goals in synthetic chemistry is to obtain compounds featuring unusual valence states that are stable under ambient conditions. At present, stabilizing unusual Pt(III) states is considered difficult, except through direct Pt–Pt bonding such as that in platinum-blues or organometallization using bulky ligands. Pt(III) stabilization is also very difficult in halogen-bridged metal complex chains (MX-Chains). Herein, the iodide-bridged Pt(III) dimer compound [Pt2(en)4I3]I3 (en = ethylenediamine), which is prepared by the iodine oxidation of [PtII(en)2]I2, has been successfully synthesized and characterized. This compound is stable and is obtained as diamond-shaped single crystals with a lustrous emerald-green color under reflected light and a red color under transmitted light. The Pt(III) state is stabilized by the five-center ten-electron (5c-10e) bonding in the I–Pt–I–Pt–I core, in addition to the very strong antiferromagnetic state. The stabilization mechanism of Pt(III) through a 5c-10e bonding is considered a superatom complex; thus, this work provides new insight for stabilizing the unusual Pt(III) state.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"25 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857982","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

K6NaCaRe2(B5O10)3 (Re = Y, Lu): Two NLO Compounds Exhibiting a Short Absorption Edge in the A7–xA’xAeRe2(B5O10)3 (x = 0, 1) Family

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04680

Wencong Li, Zhaowei Hu, Yanyan Ding, Yueting Zhu, Qun Jing, Lili Liu

{"title":"K6NaCaRe2(B5O10)3 (Re = Y, Lu): Two NLO Compounds Exhibiting a Short Absorption Edge in the A7–xA’xAeRe2(B5O10)3 (x = 0, 1) Family","authors":"Wencong Li, Zhaowei Hu, Yanyan Ding, Yueting Zhu, Qun Jing, Lili Liu","doi":"10.1021/acs.inorgchem.4c04680","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04680","url":null,"abstract":"The discovery and synthesis of new NLO materials in the ultraviolet (UV) region are crucial to developing laser technology. The chemical substitution strategy is an effective pathway to design potential UV or DUV NLO crystals. Herein, two new compounds, K6NaCaY2(B5O10)3 and K6NaCaLu2(B5O10)3, have been synthesized using KB5O8·4H2O as the template. Their crystal structures feature a three-dimensional (3D) [Re2(B5O10)3]∞ framework consisting of [B5O10] groups and [ReO6] octahedra, and the remainder of metal cations fill the void to control charge balance and maintain the stability of the crystal structure. Both K6NaCaY2(B5O10)3 and K6NaCaLu2(B5O10)3 crystallize in the acentric space group R32, so they exhibit an SHG effect, and the value is ∼0.5 × KDP (KH2PO4). Meanwhile, they show a phase-matching ability. Due to the participation of alkali metals, alkaline earth metal, and [B5O10] unit, the title compounds possess short absorption edges of ∼230 nm. In addition, they have high thermal stability and can be stable up to 931 °C. These results confirm the effectiveness of the chemical substitution strategy for designing NLO compounds, and then the two compounds can potentially serve as good UV NLO materials.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"97 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858022","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

Silver 4,4′-Vinylenedipyridine Coordination Polymers: Linker Effects on Formation Thermodynamics and Anion Exchange

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04146

Jeremy L. Barnett, John S. Wenger, Addis Getahun, Timothy C. Johnstone, Scott R. J. Oliver

{"title":"Silver 4,4′-Vinylenedipyridine Coordination Polymers: Linker Effects on Formation Thermodynamics and Anion Exchange","authors":"Jeremy L. Barnett, John S. Wenger, Addis Getahun, Timothy C. Johnstone, Scott R. J. Oliver","doi":"10.1021/acs.inorgchem.4c04146","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04146","url":null,"abstract":"Four new and one previously reported silver 4,4′-vinylenedipyridine (Vpe) coordination polymers were tested as anion exchange materials to assess their potential for pollutant sequestration and compared to analogous silver 4,4′-bipyridine (bipy) coordination polymers. The materials were synthesized using nitrate, tetrafluoroborate, perchlorate, perrhenate, or chromate as the anion to produce cationic coordination polymers with solubilities ranging from 0.0137(7) to 0.21(5) mM. These values are much lower than silver bipy coordination polymers [0.045(3) to 5.5(5) mM] and agree with thermochemical calculations. [Ag(Vpe)+][BF4–], [Ag2(Vpe)2.52+][CrO42–]·5H2O, and [Ag(Vpe)+][ReO4–]·2H2O structures are reported. Perrhenate and chromate ions in an equimolar solution were fully adsorbed by [Ag(Vpe)+][NO3–]·3H2O [620(2) and 137.1(6) mg/g, respectively] as well as by [Ag(Vpe)+][BF4–] [661.8(3) and 190(3) mg/g, respectively] via anion exchange. DFT calculations show that torsional energetics play a significant role in the formation thermodynamics by reducing the energy cost by as much as 4.8 kJ/mol when bipy is replaced with Vpe in silver-based coordination polymers. The results obtained with the flat Vpe ligand highlight the potential role of coordination polymers in practical anion exchange.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858015","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

MER Zeolite with Remarkable Pb2+ and Cd2+ Removal Capability Cost-Effectively Synthesized from Postprocessed Natural Stellerite

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04717

Yufei Wang, Shuang Liu, Junyao Pan, Haoyang Zhang, Binyu Wang, Wenfu Yan

{"title":"MER Zeolite with Remarkable Pb2+ and Cd2+ Removal Capability Cost-Effectively Synthesized from Postprocessed Natural Stellerite","authors":"Yufei Wang, Shuang Liu, Junyao Pan, Haoyang Zhang, Binyu Wang, Wenfu Yan","doi":"10.1021/acs.inorgchem.4c04717","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04717","url":null,"abstract":"MER zeolite, a low-silica zeolite with an 8-membered ring aluminosilicate framework, has been recognized as a promising material in sorption, separation, and ion-exchange applications. Herein, we developed a cost-effective and rapid method to convert parent zeolite H-STI, which was derived from natural stellerite, into MER zeolite through interzeolite conversion with a crystallization time of 8 h. This MER zeolite exhibits high efficiency in removing Pb2+ and Cd2+ from simulated heavy metal wastewater over a pH range of 3–8. It also shows excellent selectivity in the presence of competitive cations, including Na+, K+, Ca2+, Mg2+, Zn2+, Cu2+, and Co2+. At 25 °C, with a MER-S dosage of 1/3000 g·mL–1 for Pb2+ and 1/500 g·mL–1 for Cd2+, the removal efficiencies were 99.7 and 99.9%, respectively. The distribution coefficients were 1097 L·g–1 for Pb2+ and 550 L·g–1 for Cd2+, and the sorption capacities reached 513 mg·g–1 for Pb2+ and 171 mg·g–1 for Cd2+, indicating that the product MER zeolite is one of the highest sorbents for Pb2+ and Cd2+ reported for zeolitic materials. The sorption for Pb2+ and Cd2+ both follows the chemisorption-dominated mechanism, driven by the ion-exchange process between the K+ in the channels MER-S and the Pb2+ or Cd2+ in solution. This work highlights the potential of rapidly synthesized MER zeolite for the effective removal of heavy metal cations, emphasizing its performance and practical applicability.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858016","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

Assembling the Puzzle of Coparsite Polymorphism: Synthesis, Thermal Expansion, and Quantum Magnetism of α- and β-Cu4O2(VO4)Cl 拼凑铜绿石多态性之谜：α- 和 β-Cu4O2(VO4)Cl 的合成、热膨胀和量子磁性α-和β-Cu4O2(VO4)Cl的合成、热膨胀和量子磁性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c03694

Victoria A. Ginga, Oleg I. Siidra, Alexander A. Tsirlin, Annette Setzer

{"title":"Assembling the Puzzle of Coparsite Polymorphism: Synthesis, Thermal Expansion, and Quantum Magnetism of α- and β-Cu4O2(VO4)Cl","authors":"Victoria A. Ginga, Oleg I. Siidra, Alexander A. Tsirlin, Annette Setzer","doi":"10.1021/acs.inorgchem.4c03694","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03694","url":null,"abstract":"Two new dimorphic spin–1/2 quantum magnets, α- and β-Cu4O2(VO4)Cl, were synthesized via a chemical vapor transport method that emulates mineral formation in volcanic fumaroles. α-Cu4O2(VO4)Cl (1) is a pure vanadate analogue of the coparsite mineral characterized by [O2Cu4]4+ 1D single rods, whereas β-Cu4O2(VO4)Cl (2) adopts a new structure type with the [O2Cu4]4+ 2D layered topology. The thermal expansions of both 1 and 2 studied by high-temperature single-crystal X-ray diffraction are reported. Using ab initio calculations, we infer the presence of antiferromagnetic Cu1–Cu3 units with strong couplings on the order of 200–400 K forming chains (1) and layers (2). The Cu2 atoms are weakly coupled to such units. Magnetic susceptibility measurements corroborate this scenario by showing deviations from the paramagnetic behavior even at 300 K. Moreover, 1 reveals an antiferromagnetic ordering below TN = 24 K with a weak uncompensated magnetic moment.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"92 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849229","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

Enhancing the Electrochemical Energy Storage of Metal–Organic Frameworks: Linker Engineering and Size Optimization

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04771

Xinxin Hang, Xiaoju Wang, Jiaxin Chen, Meng Du, Yangyang Sun, Yong Li, Huan Pang

{"title":"Enhancing the Electrochemical Energy Storage of Metal–Organic Frameworks: Linker Engineering and Size Optimization","authors":"Xinxin Hang, Xiaoju Wang, Jiaxin Chen, Meng Du, Yangyang Sun, Yong Li, Huan Pang","doi":"10.1021/acs.inorgchem.4c04771","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04771","url":null,"abstract":"The electric conductivity and charge transport efficiency of metal–organic frameworks (MOFs) dictate the effective utilization of built-in redox centers and electrochemical redox kinetics and therefore electrochemical performance. Reticular chemistry and the tunable microcosmic shape of MOFs allow for improving their electric conductivity and charge transfer efficiency. Herein, we synthesized two Ni-MOFs (Ni-tdc-bpy and Ni-tdc-bpe) by the solvothermal reaction of Ni2+ ions with 2,5-thiophenedicarboxylic acid (H2tdc) in the presence of conjugated 4,4′-bipyridyl (bpy) and 1,2-di(4-pyridyl)ethylene (bpe) coligands, respectively. We also synthesized two thinning Ni-MOFs (Ni-tdc-bpy(0.5) and Ni-tdc-bpe(0.5)) by adjusting the amounts of bpy and bpe, respectively. Experimental investigations revealed that linker engineering by tuning the delocalization of the N-donor dipyridyl coligands and size optimization by controlling the amount of the coligand rendered the Ni-MOF with significantly improved electrical conductivity and charge transport efficiency. Among them, Ni-tdc-bpe(0.5) possessing the bpe coligand with more strong delocalization and an optimized size exhibited an enhanced specific capacitance of 650 F g–1 at 0.5 A g–1. Moreover, the hybrid supercapacitor constructed from Ni-tdc-bpe(0.5) and activated carbon delivered an excellent energy density of 33.6 Wh kg–1 at a power density of 232.6 W kg–1.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"63 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849234","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

High-Quantum-Efficiency Pr3+-Doped Li7La3Zr2O12 Garnet and Associated Temperature-Sensing Performance

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04336

Yihao Shen, Xiangyu Han, Shuxian Wang, Haohai Yu, Huaijin Zhang

{"title":"High-Quantum-Efficiency Pr3+-Doped Li7La3Zr2O12 Garnet and Associated Temperature-Sensing Performance","authors":"Yihao Shen, Xiangyu Han, Shuxian Wang, Haohai Yu, Huaijin Zhang","doi":"10.1021/acs.inorgchem.4c04336","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04336","url":null,"abstract":"The understanding of energy transfer mechanisms between different excited states of Pr3+ is closely bound up with exploiting high-quantum-efficiency Pr3+-doped luminescent thermometers and optimizing their temperature-sensing performances. Herein, we propose a new-type Pr3+-doped tetragonal-phase Li7La3Zr2O12 (Pr3+:LLZO) garnet luminescent thermometer and study accompanied photoluminescence (PL) properties. Combining composition optimization, we gain a fantastic room-temperature PL quantum efficiency within Pr3+:LLZO phosphors (77.48%), a value obviously superior to those of traditional Pr3+-doped garnet-type phosphors. The thermally induced fluorescence quenching of 3P0 emissions within Pr3+:LLZO mainly originates from phonon-assisted thermal ionization, differing from the Pr3+-doped Y3Al5O12 garnet. By contrast, the 1D2 case is akin to most Pr3+-doped materials in that the quenching behavior is seriously associated with the cross-relaxation between the 3P0 and 1D2 states. On that basis, we propose a Pr3+:LLZO luminescence thermometry strategy by utilizing different quenching mechanisms of steady-state 3P0 and 1D2 emissions, performing a comparable temperature-sensing capability to those Pr3+-based garnet-type luminescent thermometers. Our findings strengthen the importance of discerning the quenching mechanisms of Pr3+ emissions and provide a valuable perspective for designing high-quantum-efficiency Pr3+-doped garnet-type luminescent materials and relevant luminescence thermometry.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"114 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857983","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

Highly Stable Lanthanide-Organic Frameworks Based on {Ln6O8} Clusters with Photocatalytic Reduction of CO2 to CO 基于 {Ln6O8} 的高稳定镧系有机框架，具有光催化将 CO2 还原成 CO2 的能力光催化将 CO2 还原成 CO

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c03799

Kang-Le Xie, Li-Ping Wu, Ya-Qing Liao, Jun-Jie Hu, Kang-Qiang Lu, He-Rui Wen, Jin-Rong Huo

{"title":"Highly Stable Lanthanide-Organic Frameworks Based on {Ln6O8} Clusters with Photocatalytic Reduction of CO2 to CO","authors":"Kang-Le Xie, Li-Ping Wu, Ya-Qing Liao, Jun-Jie Hu, Kang-Qiang Lu, He-Rui Wen, Jin-Rong Huo","doi":"10.1021/acs.inorgchem.4c03799","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c03799","url":null,"abstract":"Metal–organic frameworks (MOFs) with adjustable structures, diverse chemical functionalities, and excellent CO2 capture ability have shown important potential application in the photocatalytic reduction of CO2 to valuable fuel to curb the energy crisis. In this work, a series of new isostructural lanthanide-organic frameworks based on hexanuclear {Ln6O8} clusters, {(DMA)2 [Ln6(μ3–OH)8(H2O)6(SBTC)3]}n (Ln-MOFs, Ln = Eu, Dy, Gd, Tb, Yb; H4SBTC = 5,5′-(ethene-1,2-diyl) di-isophthalic acid; DMA = dimethylamine cation) were synthesized by the solvothermal method. Ln-MOFs were metal–organic frameworks formed by {Ln6(μ3–OH)8} clusters and poly(carboxylic acid) ligands H4SBTC, which exhibited excellent photocatalytic properties for the reduction of CO2 to CO. Among these Ln-MOFs, the production rate of photocatalytic reduction of CO2 to CO by Eu-MOF was 663.00 μmol·h–1·g–1 and the selectivity reached 94.2%, utilizing [Ru(bpy)3]Cl2·6H2O as photosensitizers. Experimental characterizations and density functional theory (DFT) calculations unveiled that the effective charge separation, strong CO2 binding affinity, weak H2O adsorption energy, as well as low reaction energy barriers for the *COOH intermediates over Eu-MOF play an important role in possessing superior photoactivity. This study provides insights into the field of Ln-MOF materials for efficient photocatalytic CO2 reduction and conversion applications.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"23 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849231","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

Trends in Methanol-Solvated Actinide Ions and Actinide Expanded Porphyrin Complexes 甲醇溶解放线离子和放线扩增卟啉络合物的发展趋势

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-19 DOI: 10.1021/acs.inorgchem.4c04503

Meagan S. Oakley, Georg Schreckenbach

{"title":"Trends in Methanol-Solvated Actinide Ions and Actinide Expanded Porphyrin Complexes","authors":"Meagan S. Oakley, Georg Schreckenbach","doi":"10.1021/acs.inorgchem.4c04503","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04503","url":null,"abstract":"Trivalent actinide expanded porphyrin complexes have been of synthetic interest since the isolation of the series of trivalent lanthanide texaphyrin complexes in 1992, however, synthesis of these actinide-based complexes has not yet been achieved. In this work, a computational study with relativistic density functional theory was performed to determine how trivalent actinide ions (Ac3+ through Lr3+) interact with Schiff base expanded porphyrin macrocycles in a methanol solvent as an alternate pathway to stabilization. A thorough analysis of structural parameters, electronic structure, stability of microsolvation environments, and relative binding energies provided insight into the most stable structures. Trends in bonding and structure for the full actinide series are reported for methanol solvated ions, which reports actinide contraction along the series for early and mid actinides. Texaphyrin incorporates the actinide ions in a planar fashion, whereas for alaskphyrin a bent structure is more favorable; this bend results in stronger interaction energies than those calculated for the texaphyrin complexes. We also show that the redox-active expanded porphyrin ligands are able to accommodate a variety of actinides through charge transfer stabilization. Based on relative binding energy and energy decomposition analysis, it was found that texaphyrin and alaskaphyrin both exhibit a strong preference for binding to Th.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"472 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849232","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

(RPh3P)[Mn(dca)3]: A Family of Glass-Forming Hybrid Organic–Inorganic Materials (RPh3P)[Mn(dca)3]：玻璃成型有机-无机杂化材料家族

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2024-12-18 DOI: 10.1021/acs.inorgchem.4c04181

Bikash Kumar Shaw, Lucia Corti, Joshua M. Tuffnell, Celia Castillo-Blas, Patrick Schlachta, Georgina P. Robertson, Lauren McHugh, Adam F. Sapnik, Sebastian A. Hallweger, Philip A. Chater, Gregor Kieslich, David A. Keen, Sian E. Dutton, Frédéric Blanc, Thomas D. Bennett

{"title":"(RPh3P)[Mn(dca)3]: A Family of Glass-Forming Hybrid Organic–Inorganic Materials","authors":"Bikash Kumar Shaw, Lucia Corti, Joshua M. Tuffnell, Celia Castillo-Blas, Patrick Schlachta, Georgina P. Robertson, Lauren McHugh, Adam F. Sapnik, Sebastian A. Hallweger, Philip A. Chater, Gregor Kieslich, David A. Keen, Sian E. Dutton, Frédéric Blanc, Thomas D. Bennett","doi":"10.1021/acs.inorgchem.4c04181","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04181","url":null,"abstract":"ABX3-type hybrid organic–inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPh3P)[Mn(dca)3] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196–237 °C (Tm) and then vitrify upon cooling to room temperature, forming glasses. In situ glass formation of this new family of materials was probed on a large scale using a variable-temperature PXRD experiment. Structure analyses of the crystalline and the glasses were carried out by solid-state nuclear magnetic resonance spectroscopy and synchrotron X-ray total scattering techniques for using the pair distribution function. The mechanical properties of the glasses produced were evaluated showing promising durability. Thermal and electrical conductivities showed low thermal conductivities (κ ∼ 0.07–0.09 W m–1 K–1) and moderate electrical conductivities (σ ∼ 10–4–10–6 S m–1) at room temperature, suggesting that by the precise control of the A cation, we can tune meltable hybrid structures from moderate conductors to efficient thermal insulators. Our results raise attention on the practical use of this new hybrid material in applications including, e.g., photovoltaic devices to prevent light-deposited heat (owing to low κRT), energy harvesting thermoelectric, etc., and advance the structure–property understanding.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"92 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142849362","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