Dalton Transactions最新文献_第6页

Influence of triphosphine ligand coordination geometry in Mn(I) hydride complexes [(P∩P∩P)(CO)2MnH] on their kinetic hydricity 氢化物锰（I）配合物[(P∩P∩P)(CO)2MnH]中三膦配体的配位几何对其动力学水合性的影响

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-06 DOI: 10.1039/d4dt02496f

Sergey A. Kovalenko, Ekaterina S. Gulyaeva, Elena S. Osipova, Oleg A. Filippov, Anastasia Danshina, Laure Vendier, Nikolay V. Kireev, Ivan A. Godovikov, Yves CANAC, Dmitry A. Valyaev, Natalia Belkova, Elena Shubina

{"title":"Influence of triphosphine ligand coordination geometry in Mn(I) hydride complexes [(P∩P∩P)(CO)2MnH] on their kinetic hydricity","authors":"Sergey A. Kovalenko, Ekaterina S. Gulyaeva, Elena S. Osipova, Oleg A. Filippov, Anastasia Danshina, Laure Vendier, Nikolay V. Kireev, Ivan A. Godovikov, Yves CANAC, Dmitry A. Valyaev, Natalia Belkova, Elena Shubina","doi":"10.1039/d4dt02496f","DOIUrl":"https://doi.org/10.1039/d4dt02496f","url":null,"abstract":"Octahedral Mn(I) complexes bearing tridentate donor ligands [(L∩L’∩L’’)(CO)2MnX] have recently emerged as major players in catalytic (de)hydrogenation processes. While most of these systems are still based on structurally rigid pincer scaffolds imposing a meridional coordination mode, for some more flexible tridentate ligands a facial arrangement of donor moieties becomes possible. Accordingly, the geometry of the corresponding Mn(I) hydrides [(L∩L’∩L’’)(CO)2MnH] directly involved in the catalytic processes, namely the nature of the donor extremity located in the trans-position of the hydride (CO and L for mer- and fac-configuration, respectively) may influence their hydride transfer ability. Herein, low-temperature IR and NMR spectroscopy studies of two model Mn(I) complexes mer-[(L1)(CO)2MnH] and fac-[(L2)(CO)2MnH] bearing similar triphosphine ligands (L1 = PhP(CH2CH2PPh2)2; L2 = MeC(CH2PPh2)3) in the presence of B(C6F5)3 as H− abstractor revealed for the first time a higher kinetic hydricity of the tripodal system. Even for the pincer complex, hydride transfer proceeds from the non-covalent adduct fac-[(L1)(CO)2MnH]∙∙∙B(C6F5)3 with facial geometry arising from the mer-to-fac isomerization of the initial mer-[(L1)(CO)2MnH]. The higher reactivity of the fac-hydride derivatives was found to be consistent with catalytic performance of the corresponding Mn(I) bromide complexes in the benchmark ester hydrosilylation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

A new type of Lanthanide−sodium metalloring organic framework featuring high proton conduction in a wide temperature range and detection of Fe3+ ions 一种新型镧系钠金属有机框架，具有在宽温度范围内高质子传导性和检测 Fe3+ 离子的特点

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt02479f

Lizhen Liu, Gaoyong Zhu, Kang Yang, Yaozong Chen, Yuan Hong, Yiyang Bo, Susu Wu, Xiangfang Peng, Zizhu Yao

{"title":"A new type of Lanthanide−sodium metalloring organic framework featuring high proton conduction in a wide temperature range and detection of Fe3+ ions","authors":"Lizhen Liu, Gaoyong Zhu, Kang Yang, Yaozong Chen, Yuan Hong, Yiyang Bo, Susu Wu, Xiangfang Peng, Zizhu Yao","doi":"10.1039/d4dt02479f","DOIUrl":"https://doi.org/10.1039/d4dt02479f","url":null,"abstract":"We present the design and synthesis of two novel isostructural metalloring organic frameworks (MROFs) {[(Me2NH2)1.25(H3O)4.25Na1.5X2(μ2-OH)(H2O)(SIP)4]n • x sol (FUT-2-X, X = Eu, Sm), which are composed of sulfonate-carboxylate ligand 5-sulfoisophthalic acid monosodium salt (NaH2SIP) and unprecedented Lanthanide - sodium metalloring [X4Na4(H2O)(SIP)2, X = Eu, Sm]. The two MROFs possess channel walls decorated with uncoordinated sulfonic acid groups and filled with abundant guest molecules residing within the framework, which support the proton conductivity of the materials by expanding the intermolecular hydrogen bonding network. FUT-2-Eu exhibits exceptional proton conductivity over a wide temperature range, achieving conductivity from 1.91×10-5 S cm-1 (-40 oC) to 2.65 × 10-3 S cm-1 (90 oC). Thanks to the dominant role of the additional guest H2O molecules in FUT-2-Eu's channels, which facilitate the formation of hydrogen-bonded networks for ultra-fast proton transfer with low energy barriers, FUT-2-Eu outperforms FUT-2-Sm in both operating temperature range and proton conductivity. It is worth noting that FUT-2-Eu has the widest operating temperature range among proton conduction materials of MROFs. Furthermore, FUT-2-Eu can be considered as an excellent luminescence sensor with high sensitivity (Ksv = 1.66 × 104 L·mol-1) and low detection limit (3.64 μM) for detecting Fe3+.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574323","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Influence of weakly coordinating anions binding to the hexa-tert-butyl dysprosocenium cation 弱配位阴离子与六叔丁基镝阳离子结合的影响

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt02713b

Sophie C. Corner, Gemma Kate Gransbury, David P Mills

{"title":"Influence of weakly coordinating anions binding to the hexa-tert-butyl dysprosocenium cation","authors":"Sophie C. Corner, Gemma Kate Gransbury, David P Mills","doi":"10.1039/d4dt02713b","DOIUrl":"https://doi.org/10.1039/d4dt02713b","url":null,"abstract":"Complexes containing isolated dysprosocenium cations, [Dy(CpR)2][WCA] (CpR = substituted cyclopentadienyl, WCA = weakly coordinating anion), have recently emerged as leading examples of high-temperature single-molecule magnets (SMMs) due to a combination of the axial orientation and rigidity of the CpR rings. However, our understanding of the effects of transverse fields on the magnetic properties of [Dy(CpR)2]+ cations is underdeveloped. Here we investigate the impact of equatorially-bound WCAs via the synthesis of the Dy(III) bis-CpR complexes [Dy(Cpttt)2{AlCl[OC(CF3)3]3-κ-Cl}] (1) and [Dy(Cpttt)2{AlCl(C2H5)[OC(C6F5)3]2-κ-Cl}] (2), and their characterisation by single crystal XRD, elemental analysis, ATR-IR and NMR spectroscopy, and ab initio calculations. Despite the similarity of the Dy coordination spheres in 1 and 2 we find that their effective energy barriers to reversal of magnetisation are vastly different (Ueff = 886(17) cm–1 and 559(18) cm–1, respectively) and they both show waist-restricted magnetic hysteresis at 2 K. Together, these data provide fresh insights into the sensitivity of the magnetic properties of [Dy(CpR)2]+ cations to relatively weak equatorial interactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Doping induced band-gap shrinkage to modify electronic structure of MoS2 for organic wastewater management 掺杂诱导带隙收缩，改变用于有机废水处理的 MoS2 电子结构

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt00523f

Yuchen Zhang, Yuehan Jia, Yanjie Li, Hongquan Xu, Jingsu Wang, Maobin Wei, Yong Zhang, Hui Yuan, Ming Gao

{"title":"Doping induced band-gap shrinkage to modify electronic structure of MoS2 for organic wastewater management","authors":"Yuchen Zhang, Yuehan Jia, Yanjie Li, Hongquan Xu, Jingsu Wang, Maobin Wei, Yong Zhang, Hui Yuan, Ming Gao","doi":"10.1039/d4dt00523f","DOIUrl":"https://doi.org/10.1039/d4dt00523f","url":null,"abstract":"MoS2, with its high specific surface area and tunable electronic structure, has received much interest in the fields of sensing and environmental remediation. Nevertheless, pure MoS2 has the disadvantages of easy aggregation and the high electron-hole pairs complexity, which affects its SERS and photocatalytic performance. In this work, band-gap shrinkage strategy was used to improve MoS2 performance for SERS and photocatalytic applications. It exhibited high SERS activity (enhancement factor (EF) = 3.61 × 108), great stability (4 mth), broad universality (CV, CR and R6G), and excellent reusability (recover 95% after 5 cycles). In addition, the interfacial dipole-dipole interaction and charge transfer (CT) process caused by doping Ru together enhance the SERS sensitivity, and the limit of detection of CV is down to 10-11 M. The degradation rate of 10-5 M CV was up to 99% after 60 min of Ru-MoS2 photocatalytic degradation under visible light. This study investigated the effect of doping-induced bandgap shrinkage on charge transfer (CT), providing new insights into improving the sensitivity of semiconductors SERS substrates for efficient low-concentration SERS detection and low-cost sustainable wastewater remediation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580255","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Noble Metal-Free Porphyrin Covalent Organic Framework Membrane for CO2 Photoreduction to CO 用于将 CO2 光还原为 CO 的无贵金属卟啉共价有机框架膜

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt02658f

Yuxia Hou, Haizeng Ma, Dan Zhu, Renlong Li, ZIyan Zhao, Chun-Xiang Li, Cheng-Xing Cui, Ji-Chao Wang

引用次数: 0

Heats of Formation on the Way from B2H6 to B20H16: Thermochemical Consequences of Multicenter Bonding in Ab initio and DFT Methods 从 B2H6 到 B20H16 的形成热： Ab initio 和 DFT 方法中多中心键合的热化学后果

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt02589j

Jindrich Fanfrlik, Jan Řezáč, Drahomír Hnyk, Josef Holub

引用次数: 0

Multifunctional chiral metal hydrogen-bonded organic frameworks constructed from lanthanide ions with trigonal prismatic coordination environment 由具有三棱柱配位环境的镧系离子构建的多功能手性金属氢键有机框架

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt02131b

Guo Peng, Guoxing Zhou, Xiang Tao Dong, Yong-Bo Peng, Rong-Yan Zhang, Ying-Zhao Ma, Xiaoming Ren

引用次数: 0

One-pot facile synthesis of rod-like Bi2S3 particle in deep eutectic solvent and its ppb-level selective H2S gas detection 在深共晶溶剂中一锅简易合成棒状 Bi2S3 粒子及其ppb 级选择性 H2S 气体检测技术

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-05 DOI: 10.1039/d4dt03006k

Reiko Furukawa, Takuya Hasegawa, Ayahisa Okawa, Shu Yin

引用次数: 0

Crystalline bilayer formation in homoleptic low-spin Fe(II) compounds with alkyl chain substituents. 具有烷基链取代基的同色低自旋铁（II）化合物中结晶双层的形成。

IF 3.5 3区化学

Dalton Transactions Pub Date : 2024-11-04 DOI: 10.1039/d4dt02667e

Blaise L Geoghegan, Spyridon Koutsoukos, Wasinee Phonsri, Keith S Murray, Peter J Cragg, Marcus K Dymond, Ian A Gass

{"title":"Crystalline bilayer formation in homoleptic low-spin Fe(II) compounds with alkyl chain substituents.","authors":"Blaise L Geoghegan, Spyridon Koutsoukos, Wasinee Phonsri, Keith S Murray, Peter J Cragg, Marcus K Dymond, Ian A Gass","doi":"10.1039/d4dt02667e","DOIUrl":"https://doi.org/10.1039/d4dt02667e","url":null,"abstract":"A series of asymmetric, homoleptic Fe(II) compounds based on the facially-binding tridentate ligand N-methyl-1,1-di(pyridin-2-yl)Cn-amine (LCn) (Cn = butyl, hexyl, octyl, decyl, dodecyl, tetradecyl and hexadecyl alkyl chains) with formula [FeII(LCn)2](X)2·solvate, where n = 4, 14 and X = BF4 (1C4 and 1C14) or n = 6, 8, 10, 12, 16 and X = CF3SO3 (1C6-1C12 and 1C16), are reported. Complexes 1C6 to 1C16 pack in crystalline bilayers in the solid state, forming hydrophobic and hydrophilic regions between adjacent layers of complexes. The combination of short Fe-N bond distances (∼2.00 Å) and SQUID magnetic susceptibility measurements show that the complexes are in the low-spin state across all measured temperature ranges. Differential scanning calorimetry confirmed phase transitions occur in compounds 1C6, 1C12, 1C14 and 1C16 upon heating from room temperature. The lack of any spin transitions and thermal stability conferred by thermogravimetric analysis over this temperature range suggest that these transitions are crystallographic in nature. 1H NMR studies show that the low-spin Fe(II) centres undergo partial conversion to paramagnetic species in solution. UV-vis spectroscopy in a range of common organic solvents show that the central Fe ions remain in the +2 oxidation state, suggesting that the increase in magnetic susceptibility in solution is likely due to partial spin-crossover, or due to speciation, in which a proportion of the compounds are high-spin Fe(II) complexes.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142566395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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

Morphology-dependent Li+ ion dynamics in X-ray amorphous and crystalline Li3PS4 prepared by solvent-assisted synthesis 溶剂辅助合成法制备的 X 射线无定形和晶体 Li3PS4 中与形态有关的 Li+ 离子动力学

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-04 DOI: 10.1039/d4dt02636e

Jonas Spychala, Christoph Mandl, Katharina Hogrefe, Martin Wilkening, Bernhard Gadermaier

{"title":"Morphology-dependent Li+ ion dynamics in X-ray amorphous and crystalline Li3PS4 prepared by solvent-assisted synthesis","authors":"Jonas Spychala, Christoph Mandl, Katharina Hogrefe, Martin Wilkening, Bernhard Gadermaier","doi":"10.1039/d4dt02636e","DOIUrl":"https://doi.org/10.1039/d4dt02636e","url":null,"abstract":"Solid-state electrolytes with high ionic conductivity will be crucial for future energy storage systems. Among many possible materials, thiophosphates offer both favourable mechanical properties and fast ionic transport. β-Li3PS4, as a member of the thiophosphate family, has gained recent attention, due to its remarkable increase in Li+ ionic conductivity when prepared via solvent-assisted synthesis. Despite earlier studies, the lithium ion migration processes causing the increased conductivity remain, however, still uncertain. Here, we study both long-range cation transport and local Li+ jump processes by broadband impedance spectroscopy and nuclear magnetic resonance (NMR), respectively. In particular, we focus on the comparison between mechanochemical and solvent-assisted synthesis to determine the origin of the increased ionic conductivity observed in the latter. Our measurements reproduce the previously reported high ionic conductivity and reveal that synthesis conditions significantly affect the Arrhenius pre-exponential factor governing ionic conductivity. Diffusion-controlled 7Li (and 31P) NMR spin relaxation rates confirm rapid, anisotropic lithium ion hopping that is characterized by timescale-dependent activation energies Ea ranging from 0.40 eV (long-range transport, as also seen by conductivity spectrosocpy) to values down to 0.09 eV (local barries).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574326","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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