Dalton Transactions最新文献_第8页

Synthesis and anion binding properties of (thio)urea functionalized Ni(II)-salen complexes. (硫)脲官能化 Ni(II)-salen 复合物的合成与阴离子结合特性。

IF 3.5 3区化学

Dalton Transactions Pub Date : 2024-11-01 DOI: 10.1039/d4dt02683g

Jae Elise L Payong, Nadia G Léonard, Lauren M Anderson-Sanchez, Joseph W Ziller, Jenny Y Yang

{"title":"Synthesis and anion binding properties of (thio)urea functionalized Ni(II)-salen complexes.","authors":"Jae Elise L Payong, Nadia G Léonard, Lauren M Anderson-Sanchez, Joseph W Ziller, Jenny Y Yang","doi":"10.1039/d4dt02683g","DOIUrl":"https://doi.org/10.1039/d4dt02683g","url":null,"abstract":"Salen ligands (salen = N,N'-ethylenebis(salicylimine)) are well-known for their versatility and widespread utility in chelating metal complexes. However, installation of hydrogen-bonding units on the salen framework, particularly functional groups that require amine-based precursors such as (thio)ureas, is difficult to achieve without the use of protecting group strategies. In this report, we show that the phenylketone analog of salicyladehyde is a stable alternative that enables the facile installation of hydrogen bonding (thio)urea groups on the salen scaffold, thus imparting anion binding abilities to a metal salen complex. Synthesis of symmetric N-phenyl(thio)urea salen ligands functionalized at the 3,3'-position and an unsymmetric salen ligand with N-phenylurea at the 5-position was achieved. Subsequent metalation with nickel(II) acetate afforded the nickel(II) complexes that were investigated for their anion binding properties towards F-, Cl-, Br-, CH3COO-, and H2PO4-. Solid-state structures of the nickel(II) complexes as well as the Cl- bound dimer of the symmetric urea complex were obtained. The unusual acidity of the (thio)urea groups is reflected in the pKa-dependent anion binding behavior of the nickel(II) complexes, as elucidated by 1H and 19F Nuclear Magnetic Resonance (NMR) spectroscopy and Diffusion Ordered Spectroscopy (DOSY) experiments.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556586","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

Accelerating the reaction kinetics of Ni1-xO/Ni(OH)2/NF by defect engineering for urea-assisted water splitting 通过缺陷工程加速 Ni1-xO/Ni(OH)2/NF 的反应动力学，实现脲辅助水分离

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-01 DOI: 10.1039/d4dt02871f

Yuan Rui, Zong Li, Miaohui Wang, Yunxia Liu, Haiping Lin, Peipei Huang, Qing Li

{"title":"Accelerating the reaction kinetics of Ni1-xO/Ni(OH)2/NF by defect engineering for urea-assisted water splitting","authors":"Yuan Rui, Zong Li, Miaohui Wang, Yunxia Liu, Haiping Lin, Peipei Huang, Qing Li","doi":"10.1039/d4dt02871f","DOIUrl":"https://doi.org/10.1039/d4dt02871f","url":null,"abstract":"Developing electrocatalysts with fast reaction kinetics for urea oxidation reaction (UOR) in the field of sustainable hydrogen production through urea-assisted water splitting remains challenging. Here, Ni1-xO/Ni(OH)2 supported on nickel foam (Ni1-xO/Ni(OH)2/NF) is prepared via a defect engineering strategy by combining Zn doping and acid etching. Doped Zn species are partially removed, facilitating the formation of NiOOH during the acid etching. Residual Zn species modulate the electronic structure of nickel sites, which intrinsically accelerate the reaction kinetics of Ni1-xO/Ni(OH)2/NF. Ni1-xO/Ni(OH)2/NF exhibits excellent performances for UOR with a low potential of 1.346 V versus reversible hydrogen electrode to attain 100 mA cm-2, fast reaction kinetics (18.7 mV dec-1), and excellent stability in the alkaline electrolyte. The enhanced reaction kinetics of Ni1-xO/Ni(OH)2/NF are clearly elucidated by operando electrochemical impedance spectroscopy and in-situ Raman spectra investigations. Our study offers an effective approach to design promising Ni-based UOR catalysts for the practical application of urea-assisted water splitting.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561797","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

Synthesis and Electrochemical Properties of Molybdenum Nitrido Complexes Supported by Redox-Active NHC and MIC Ligands 氧化还原活性 NHC 和 MIC 配体支持的氮化钼配合物的合成与电化学性质

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-01 DOI: 10.1039/d4dt02405b

Daniel Leitner, Florian Rochus Neururer, Stephan Hohloch

{"title":"Synthesis and Electrochemical Properties of Molybdenum Nitrido Complexes Supported by Redox-Active NHC and MIC Ligands","authors":"Daniel Leitner, Florian Rochus Neururer, Stephan Hohloch","doi":"10.1039/d4dt02405b","DOIUrl":"https://doi.org/10.1039/d4dt02405b","url":null,"abstract":"We report the synthesis of a series of molybdenum nitrido complexes supported by bis-phenolate N-heterocyclic and mesoionic carbenes. Reaction between MoN(OtBu)3 and the corresponding azolium salts [H3L1]Cl and [H3L2]Cl (with L1 = bis-phenolate triazolylidene and L2 = bis-phenolate benzimidazolylidene) gives clean access to the corresponding NHC/MIC complexes 1-Cl and 2-Cl. Electrochemical investigations of these complexes showed they can be reversible reduced at potentials of -1.13 and -1.01 V vs. Fc/[Fc]+ and the reduced complexes [1-Cl]- and [2-Cl]- can be cleanly isolated after chemical reduction with one equivalent of decamethylcobaltocene. Exchange of the halide atoms is furthermore reported to give a series of nitrido complexes supported by tert-butanolate (1-OtBu & 2-OtBu), perfluoro-tert-butanolate (1-OtBuF9 & 2-OtBuF9), tritylate (1-OCPh3 & 2-OCPh3), mesitylate (1-OMes & 2-OMes), thio-tert-butanolate (1-StBu), thiotritylate (1-SCPh3 & 2-SCPh3) and thiomesitolate complexes (1-SMes). The electrochemical properties of all complexes are evaluated and compared. All complexes isolated are characterized by multinuclear and multidimensional NMR spectroscopy and (if applicable) by EPR spectroscopy. Furthermore, the reactivity of 1-Cl and 2-Cl in the present of protons is investigated, which shows facile extrusion of ammonia in the presence of excess protons and decamethylcobaltocene yielding diamagnetic bis-molybdenum(III) complexes (3 & 4).","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561975","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

Enhanced Bi/nZVI activated molecular oxygen process for degradation of sulfonamides antibiotics in a citrate buffering system 柠檬酸盐缓冲体系中降解磺胺类抗生素的增强型 Bi/nZVI 活性分子氧工艺

IF 4 3区化学

Dalton Transactions Pub Date : 2024-11-01 DOI: 10.1039/d4dt02556c

Xiaoming Su, You Li, Ziqi Chen, Shan Jiang, Jianyu Gong

{"title":"Enhanced Bi/nZVI activated molecular oxygen process for degradation of sulfonamides antibiotics in a citrate buffering system","authors":"Xiaoming Su, You Li, Ziqi Chen, Shan Jiang, Jianyu Gong","doi":"10.1039/d4dt02556c","DOIUrl":"https://doi.org/10.1039/d4dt02556c","url":null,"abstract":"Citric acid (CA) and sodium citrate (NaCA) have been effectively employed to synergize with bismuth-doped nanoscale zero-valent iron (Bi/nZVI) to degrade sulfonamide antibiotics (SAs) without the need for additional H2O2. In the integrated Bi/nZVI-CA/NaCA system, the excellent oxidation activity of sulfamethazine (SM2), sulfadiazine (SD) and Sulfamethoxazole (SMX) in the mixed solution was obtained. The bimetallic enhancement alongside ligand complexation significantly promoted Bi/nZVI to catalyze molecular oxygen and was conducive to the spontaneous generation of H2O2. Fe(II)[Cit]− was formed in the CA/NaCA system, and then engage in Fenton-like reaction with spontaneously produced H2O2 to achieve the oxidation of SAs. Long service life was performed by the results of characterization, electrochemical analysis, utilization rate (UR), electronic efficiency (EE) and cyclic degradation experiments. In the Bi/nZVI-CA/NaCA system, two comparable degradation pathways (hydroxylation and SO2 extrusion) for SM2, SMX and SD were obtained, while another degradation pathway for SMX was reflected in the opening of the N-O bond on the benzene ring. Additionally, Post-reactive solution toxicity was assessed to ensure environmental safety. Overall, our findings provide a theoretical research basis for the effective elimination of SAs from contaminated environments.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561977","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

Rational Fabrication of Anionic Zinc Carboxylate Framework as Fluorescent Probe of 2,6-Pyridinedicarboxylic Acid 合理制备作为 2,6-吡啶二羧酸荧光探针的阴离子羧酸锌框架

IF 4 3区化学

Dalton Transactions Pub Date : 2024-10-31 DOI: 10.1039/d4dt02529f

Hui-Hui Xie, Hao Yu, Xuling Xu, Sifu Tang

引用次数: 0

The Effect of Second Coordination Sphere Interactions on the Magnetic Anisotropy of Transition Metals 第二配位层相互作用对过渡金属磁各向异性的影响

IF 4 3区化学

Dalton Transactions Pub Date : 2024-10-31 DOI: 10.1039/d4dt02873b

Sofie Stampe Leiszner, Mauro Perfetti, Emil Damgaard-Møller, Yu-Sheng Chen, Bo Brummerstedt Iversen

{"title":"The Effect of Second Coordination Sphere Interactions on the Magnetic Anisotropy of Transition Metals","authors":"Sofie Stampe Leiszner, Mauro Perfetti, Emil Damgaard-Møller, Yu-Sheng Chen, Bo Brummerstedt Iversen","doi":"10.1039/d4dt02873b","DOIUrl":"https://doi.org/10.1039/d4dt02873b","url":null,"abstract":"In the study of mononuclear transition metal Single Molecule Magnets (SMMs), extensive research has concentrated on identifying optimal coordination geometries around the central metal ion to enhance SMM properties. However, the role of non-covalent interactions in the second coordination sphere has been relatively underexplored. Here, we study the impact of non-covalent Cl---H interactions on the magnetic anisotropy of the central Co(II) ion in the distorted axially compressed octahedral complex CoCl2(tu)4 (1) (tu = S=C(NH2)2). By performing Cantilever Torque Magnetometry on 1, the orientation of the magnetic easy axis is found to deviate by almost 40° from the axial Co−Cl bond. Theoretical modelling on structural modifications of the structure of 1, quantifies how the distance between the Cl ligand and the nearest H-atom significantly influences the orientation of the magnetic easy axis and the D-value. Experimental chemical bonding analysis based on multipole modelling of synchrotron X-ray diffraction data on 1 reveal that the nearby H-atoms polarize the electron density of the Cl-ligands. This polarization results in reduced electron density in the axial positions on the Co octahedra, explaining the calculated increase in the magnitude of the D-value, when the H-atoms are moved away from Cl in silico. Topological analysis of theoretical electron densities on modified structures of 1 corroborates an increase in the electron density in the Co−Cl bond critical point, as the nearby H-atoms are moved further from Cl. These findings demonstrate the significant influence that non-covalent interactions have on the magnetic anisotropy of mononuclear transition metals and opens the possibility of utilizing these interactions in the design of transition metal based SMMs.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142555705","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

Bismuth Oxybromide Nanosheet as an Efficient Photocatalyst for Dye Degradation 用作染料降解的高效光催化剂的氧化铋纳米片

IF 4 3区化学

Dalton Transactions Pub Date : 2024-10-31 DOI: 10.1039/d4dt02180k

joy Onwumere, Rong Hua, Guojun Zhou, Haoquan Zheng, Zhehao Huang

引用次数: 0

What is the key factor affecting the cathodoluminescence intensity of europium complexes? 影响铕络合物阴极发光强度的关键因素是什么？

IF 4 3区化学

Dalton Transactions Pub Date : 2024-10-31 DOI: 10.1039/d4dt02501f

Rongdeng Lu, Tinghui Xuan, Alexander S Goloveshkin, Dmitry Kopytov, Kseniia Orekhova, Ivan Khanbekov, Valentina V. Utochnikova

引用次数: 0

CyreneTM as a green alternative to N,N’-dimethylformamide (DMF) in the synthesis of MLCT-emissive ruthenium(II) polypyridyl complexes for biological applications† CyreneTM 作为 N,N'-二甲基甲酰胺 (DMF) 的绿色替代品，用于合成 MLCT 介导的多吡啶基钌（II）络合物的生物应用†。

IF 4 3区化学

Dalton Transactions Pub Date : 2024-10-31 DOI: 10.1039/d4dt02676d

Steffan D James, Christopher E Elgar, Dandan Chen, Matthew I Lewis, Elias T. L. Ash, Dominic S Conway, Benjamin J. Tuckley, Leigh E Phillips, Natália Kolozsvári, Xiaohe Tian, Martin R Gill

{"title":"CyreneTM as a green alternative to N,N’-dimethylformamide (DMF) in the synthesis of MLCT-emissive ruthenium(II) polypyridyl complexes for biological applications†","authors":"Steffan D James, Christopher E Elgar, Dandan Chen, Matthew I Lewis, Elias T. L. Ash, Dominic S Conway, Benjamin J. Tuckley, Leigh E Phillips, Natália Kolozsvári, Xiaohe Tian, Martin R Gill","doi":"10.1039/d4dt02676d","DOIUrl":"https://doi.org/10.1039/d4dt02676d","url":null,"abstract":"Ruthenium(II) polypyridyl complexes (RPCs) that emit from triplet metal to ligand charge transfer (MLCT) states find a wide variety of uses ranging from luminophores to potential anti-cancer or anti-bacterial therapeutics. Herein we describe a greener, microwave-assisted synthetic pathway for the preparation of homoleptic [Ru(N^N)3]2+ and bis-heteroleptic [Ru(N^N)2(N^N)]2+ type complexes. This employs the bio-renewable solvent CyreneTM, dihydrolevoglucosenone, as a green alternative to N,N’-dimethylformamide (DMF) in the synthesis of Ru(N^N)2Cl2 intermediate complexes, obtaining comparable yields for N^N = 2,2’-bipyridine, 1,10-phenanthroline and methylated derivatives. Employing these intermediates, a range of RPCs were prepared and we verify that the ubiquitous luminophore [Ru(bpy)3]2+ (bpy = 2,2’-bipyridine) can be prepared by this two-step green pathway where it is virtually indistinguishable from a commercial reference. Furthermore, the novel complexes [Ru(bpy)2(10,11-dmdppz)]2+ (10,11-dmdppz = 10,11-dimethyl-dipyridophenazine) and [Ru(5,5’-dmbpy)2(10,11-dmdppz)]2+ (5,5’-dmbpy = 5,5’-dimethyl-bpy) intercalate duplex DNA with high affinity (DNA binding constants, Kb = 5.7 x107 and 1.0x107 M-1, respectively) and function as plasma membrane and nuclear DNA dyes for confocal and STED microscopies courtesy of their long-lived MLCT luminescence.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556009","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

Design and theoretical analysis of a tunable bifunctional metasurface absorber based on vanadium dioxide and photoconductive silicon 基于二氧化钒和光导硅的可调双功能超表面吸收器的设计与理论分析

IF 4 3区化学

Dalton Transactions Pub Date : 2024-10-31 DOI: 10.1039/d4dt02563f

Changfeng Fu, Xinke Wang, Yicheng Zhang, Jiaxin Ju, Wei Fan, Xiaobo Yan, Han lianfu

{"title":"Design and theoretical analysis of a tunable bifunctional metasurface absorber based on vanadium dioxide and photoconductive silicon","authors":"Changfeng Fu, Xinke Wang, Yicheng Zhang, Jiaxin Ju, Wei Fan, Xiaobo Yan, Han lianfu","doi":"10.1039/d4dt02563f","DOIUrl":"https://doi.org/10.1039/d4dt02563f","url":null,"abstract":"A tunable bifunctional metasurface absorber based on vanadium dioxide (VO2) and photoconductive silicon (PSi) is proposed in terahertz (THz) band. When the conductivities of VO2 (vo2) and PSi (PSi) are 10 S/m and 1×105 S/m, the designed absorber has a function of dual-broadband absorption. The absorptivity over 90% is in the dual-broadband of 2.47-3.71 THz and 8.90-10.62 THz, corresponding relative bandwidths (RBs) are 40.13% and 17.62%, respectively. When vo2 and PSi are equal to 2×105 S/m and 1×105 S/m, the proposed design has a function of single-broadband absorption. More than 90% absorptivity is achieved in 4.69-7.72 THz (RB=48.83%). Furthermore, the absorptivity under dual- and single-broadband is manipulated by changing PSi. Impedance matching theory, equivalent transmission-line (TL) model and electric field distribution are used to reveal the tunable bifunctional absorption mechanism. The influences of structure parameters, polarization mode and incidence angle on the dual- and single-broadband absorption are investigated. The dual- and single-broadband absorption performance is maintained within the incident angles of 55° and 60°, which also possesses polarization insensitivity. The proposed absorber has a potential application value in multifunctional devices such as modulation, sensing and electromagnetic (EM) stealth.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556010","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