Dalton Transactions最新文献

{"title":"Isolation and Characterization of the Dimetal Decacarbonyl Dication [Ru2(CO)10]2+ and the Metal-Only Lewis-Pair [Ag{Ru(CO)5}2]+","authors":"Malte Sellin, Jörg Grunenberg, Ingo Krossing","doi":"10.1039/d4dt03364g","DOIUrl":"https://doi.org/10.1039/d4dt03364g","url":null,"abstract":"The reaction of Ag<small>⁺</small> with Ru<small>₃</small>(CO)<small>₁₂</small> in CO atmosphere under concommittant irradiation with UV-light yields a salt of the metal-only Lewis-pair [Ag{Ru(CO)<small>₅</small>}<small>₂</small>]<small>⁺</small>. Switching the silver cation for a more process-selective deelectronator yields a salt of the homo-leptic transition metal carbonyl cation [Ru<small>₂</small>(CO)<small>₁₀</small>]<small>²⁺</small>, which fills the gap between the known cations [Ru(CO)<small>₆</small>]<small>²⁺</small> and [Ru<small>₃</small>(CO)<small>₁₄</small>]<small>²⁺</small>. The amount of π-backdonation in this series was studied by a combination of vibrational spectroscopy and computed relaxed force constants.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"13 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782962","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}

{"title":"Highly efficient tunable white emission with ultralong afterglow in Sb3+/Mn2+-codoped CsCdCl3 crystals for multifunctional applications","authors":"Ruonan Zhi, Linghang Kong, Hui Peng, Qilin Wei, Guang Dai, Bingsuo Zou","doi":"10.1039/d4dt03038a","DOIUrl":"https://doi.org/10.1039/d4dt03038a","url":null,"abstract":"Recently, metal halides have attracted numerous attentions due to their fascinating optical properties. However, achieving efficient white emission with ultralong afterglow remains a great challenge. Herein, we reported Sb3+/Mn2+-codoped CsCdCl3 and the multiple emission bands can be observed, which derives from the self-trapped exciton emission of Sb-Cl moiety and the d-d transition of Mn2+. Thus, the tunable emission from cyan to orange light can be obtained, and moreover, efficient white emission with a luminous efficiency of 74% is witnessed when the energy-transfer efficiency from Sb3+ to Mn2+ is 34.5%. Particularly, Sb3+/Mn2+-codoped CsCdCl3 shows the bright orange afterglow emission, and the afterglow intensity is 1000 times that of CsCdCl3 and 20 times that of CsCdCl3:Mn2+, respectively. Combined with thermoluminescence spectra, it is found that Mn2+/Sb3+ codoping can effectively regulate the depth and density distribution of trap defects, resulting in the ultralong afterglow duration exceeding 12 hours at room temperature. Surprisingly, white light stimulation can provide additional photonic energy for Sb3+/Mn2+-codoped CsCdCl3, which enables the rapid release of trapped carriers to the emission center and rejuvenates afterglow emission after 12 hours pre-delay. Finally, we demonstrated the applications of as-synthesized compounds in single-component white light illumination, multiple optical anti-counterfeiting and information encryption.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"20 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782968","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}

{"title":"Mechanism and Optimization of Ruthenium-Catalyzed Oxalamide Synthesis Using DFT","authors":"Roger Monreal-Corona, Nicolas Joly, Sylvain Gaillard, Jean-Luc Renaud, Marc Valero, Enric Mayolas, Anna Pla Quintana, Albert Poater","doi":"10.1039/d4dt03182b","DOIUrl":"https://doi.org/10.1039/d4dt03182b","url":null,"abstract":"The oxalamide skeleton is a common structural motif in many biologically active molecules. These scaffolds can be synthesized via ruthenium pincer complex-catalyzed acceptorless dehydrogenative coupling of ethylene glycol and amines. In this study, we elucidate the mechanism of this oxalamide synthesis using Density Functional Theory calculations. The rate-determining state is identified as the formation of molecular hydrogen following the oxidation of hydroxyacetamide to oxoacetamide. In predictive catalysis exercises, various modifications to the ruthenium pincer catalyst were investigated to assess their impact on the reactivity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782878","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}

{"title":"Recent advancements in metal–organic framework-based aptasensors","authors":"Zhipeng Liang, Si Chen, Chuanbin Fan, Guanghui Tian, Ziao Zong, Junli Wang, Hongming He, Hongmin Su, Feng Guo","doi":"10.1039/d4dt02959c","DOIUrl":"https://doi.org/10.1039/d4dt02959c","url":null,"abstract":"Metal–organic frameworks (MOFs), as a type of crystalline organic-inorganic hybrid materials, have demonstrated excellent performance in many fields, resulting in attracting more and more attention. Recently, MOFs have been widely used as functional materials to immobilize aptamers via various interaction forces. The MOF-based aptasensors exhibit outstanding sensing performance, including high sensitivity, excellent selectivity, and good designability, by utilizing the advantages of MOFs and aptamers. Developing MOF-based aptasensors is gradually becoming one of the important research hotspots. Herein, a comprehensive review of aptasensors based on MOFs is provided to summarize recent advancements in this field. Some representative examples are provided to discuss in detail. Furthermore, opportunities and challenges in this field are proposed in this review.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"60 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777045","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}

{"title":"Terpyridine-based ruthenium complexes containing 4,5-diazafluoren-9-one ligand with light-driven enhancement of biological activity","authors":"Francisca Mayara Santos de Alencar, Ana Cláudia Silva Gondim, Idalina Maria Moreira Carvalho, Alexandre Andrade, Luiz Gonzaga França de França Lopes, Eduardo Henrique Silva Sousa, Florencio Gouveia, Jr., Alejandro Pedro Ayala, Marcos V. Palmeira-Mello, Carlos André F Moraes, Alzir A Batista, Mayron Vasconcelos, Geângela Oliveira","doi":"10.1039/d4dt02562h","DOIUrl":"https://doi.org/10.1039/d4dt02562h","url":null,"abstract":"There has been growing effort in the scientific community to develop new antibiotics to address the major threat of bacterial resistance. One promising approach is the use of metal complexes that provide broader opportunities. Among these systems, polypyridine-ruthenium (II) complexes have received particular attention as drug candidates. Here, we prepared two new ruthenium(II) complexes with the formulation [Ru(DFO)(phtpy-R)Cl](PF6), where phtpy = 4'-phenyl-2,2': 6',2’’-terpyridine; R= -H(MPD1), -CH3(MPD2), and DFO= 4,5-diazafluoren-9-one, and investigated their chemical and biochemical activities, along with antibacterial studies. These compounds exhibit photoreactivity and produce reactive oxygen species (ROS). Photogeneration of singlet oxygen (1O2) was measured in acetonitrile with significant quantum yields using blue light, 𝛷 = 0.40 and 0.39 for MDP1 and MPD2, respectively. Further studies have shown that MPD1 can generate superoxide radicals. Antibacterial assays demonstrated a significantly enhancement in MIC (minimum inhibitory concentration) upon blue light irradiation (&gt;32-fold), with MICs of 15.6 µg/mL (S. aureus, ATCC 700698) and 3.9 µg/mL (S. epidermidis ATCC 35984) for both metal complexes. Interestingly, an MIC of 15.6 µg/mL for MPD1 and MPD2 was observed against S. epidermidis ATCC 12228 under red light irradiation. These latter results are encouraging, considering that red light penetrates deeper into the skin. In addition, no significant cytotoxicity was observed in some mammalian cells, even upon light irradiation, supporting their potential safety. Altogether, these data show evidence of the potential use of these compounds as antimicrobial photodynamic therapeutic agents, enriching our arsenal to combat this worldwide bacterial threat.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"22 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777073","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}

{"title":"Enhanced Reactivity of Cationic Au(μ-H)2MCp2 Complexes (M = Mo, W) Enabled by Bulky tris-Biaryl Phosphines","authors":"Martina Landrini, Miquel Navarro, Jesús Campos, Luca Rocchigiani","doi":"10.1039/d4dt03150d","DOIUrl":"https://doi.org/10.1039/d4dt03150d","url":null,"abstract":"[(L1)Au(µ-H)2MCp2][BF4] complexes (M = Mo, W) featuring the cavity-shaped tris-2-(4,4’-di-tert-butylbi-phenylyl)phosphine (L1) have been isolated. The tungsten derivative showed a remarkably fast reactivity in photolytic hydride transfer to generate the mononuclear gold-hydride (L1)AuH. Both bimetallic adducts trap Ag+ cations forming unprecedented {Au(u-H)M(u-H)Ag} trimetallic assemblies with destabilized Au–M interactions.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"224 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777074","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}

{"title":"Secondary Sphere Interactions Modulate Peroxynitrite Scavenging by the E2 Domain of Amyloid Precursor Protein","authors":"Eli C. Zuercher, Andrew Thomas Poore, Devendra Prajapat, Joseph M. Palazzo, Alana Thomas, Caitlin N. Birthright, Jack J. Lawrence, Ming Chen, Shiliang Tian","doi":"10.1039/d4dt02552k","DOIUrl":"https://doi.org/10.1039/d4dt02552k","url":null,"abstract":"Peroxynitrite (ONOO-) is a highly reactive nitrogen species that can cause significant damage to proteins, lipids, and DNA. Various enzymes, including metalloenzymes, play crucial roles in reducing ONOO- concentrations to protect cellular components. While the interaction of ONOO- with heme proteins is well-known, the reduction by Cu-containing proteins is less studied. The amyloid precursor protein (APP), implicated in Alzheimer's disease, has an E2 domain that binds copper ions with a dissociation constant of KD ~ 10<small>^-12</small> M and is proposed to be involved in iron homeostasis, copper trafficking, and oxidative stress response. Our recent studies using EXAFS, UV-Vis, and EPR spectroscopy revealed a previously unidentified labile water ligand in the Cu(II) site of the E2 domain, suggesting reactivity with anionic substrates like ONOO-. Experimental data showed that Cu(I)-E2 reduces ONOO- at a significant rate (1.1 x 10<small>⁵</small> M-1s-1), comparable to native peroxynitrite scavengers, while maintaining active site integrity through multiple redox cycles. This study further investigates the mechanism of ONOO- reduction by Cu(I)-E2 using the Griess assay, demonstrating that reduction occurs via single electron transfer, forming nitrite and nitrate. This process aligns with previous findings that Cu(I)-E2 is oxidized to Cu(II)-E2 upon ONOO- reduction. Mutations at Lys435, affecting secondary sphere interactions, revealed that factors beyond electrostatics are involved in substrate recruitment. MD simulations suggest that steric hindrance from a newly formed hydrogen bond also plays a role. Understanding ONOO- reduction by the E2 domain of APP expands our knowledge of copper proteins in mitigating oxidative stress and elucidates their physiological and pathological roles, particularly in Alzheimer's disease.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"13 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777043","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}

{"title":"A multi-centre metal-free COF@g-C3N4 catalyst assembled with covalent bonds for photocatalytic CO2 reduction","authors":"Xiang Wang, Zhenping Wang, Yanling Liu, Wanzhen Peng, Xiangyi Fu, Jie Zhou, Li-Zhi Han, Yingjie Hua, Zi-Yan Zhou","doi":"10.1039/d4dt02996h","DOIUrl":"https://doi.org/10.1039/d4dt02996h","url":null,"abstract":"Photocatalytic carbon dioxide (CO2) reduction technology using solar energy can convert carbon dioxide into fuels and chemicals, which is one of the most effective strategies to mitigate the energy crisis and greenhouse effect. In recent years, covalent organic frameworks (COFs) have flourished due to their unique advantages and have received extensive attention in the field of photocatalytic reduction of CO2. Here, we use the pre-designability of COF to preserve the aldehyde group at the end of COF skeleton by the motif strategy, while ensuring its excellent photosensitivity. This facilitates further assembly with amino-terminated g-C3N4 through covalent bonding, resulting in composite catalysts (COF@g-C3N4). This COF@g-C3N4 material can take g-C3N4 as the active center to undertake the main catalytic reaction function, COF as the photosensitive center to absorb light energy and generate photogenerated carriers, and covalent bonds serve as electron transport bridges, effectively facilitating the transfer of electrons. These three components operate independently yet synergistically to accomplish the photocatalytic CO2 reduction reaction. In addition, by integrating theoretical calculations with experimental results, the electron transfer and reaction mechanism in the photocatalytic process of COF@g-C3N4 were thoroughly explored, and a rational photocatalytic process was proposed. This multi-center metal-free catalyst, COF@g-C3N4, which not only has good performance in photocatalytic performance, but also is more economical and environmentally friendly, which is worthy of attention.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"4 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777069","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}

{"title":"Structural transformation from a 3D hydrophilic pillared-layered framework to 2D hydrophobic MOF nanosheets through the ligand replacement exfoliation","authors":"Po-Min Chuang, Rong-Pei Li, Jing-Yun Wu","doi":"10.1039/d3dt04379g","DOIUrl":"https://doi.org/10.1039/d3dt04379g","url":null,"abstract":"A pillared-layered metal–organic framework (MOF) {[Zn2(atpt)2(bpBTD)]∙solv}n (1), where H2atpt = 2-aminoterephthalic acid and bpBTD = bis(pyridin-4-yl)benzothiadiazole, showing pcu net topology with double interpenetration was successfully constructed. Thermally activated 1 possessed free voids of 15.3% and repeatedly exhibited a two-step CO2 adsorption isotherms over three runs, with uptakes of 138.8 cm3 g−1 STP at 195 K and P/P0 = 1. Through ligand replacement exfoliation approach, metal–organic framework (MOF) nanosheets {[Zn2(atpt)2(4-picoline)2]}n (1-ns), with 2D sql net topology, were obtained by immersing 1 in 4-picoline. Characterizations of 1-ns were achieved by energy-dispersive X-ray spectroscopy (EDS), infrared (IR) spectroscopy, X-ray powder diffraction (XRPD) patterns, and elementary analyses (EA) as well as scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). Photoluminescence spectra showed that 1 and 1-ns both emitted blue-light fluorescence in H2O. In addition, measurements on water contact angle indicated that 1 is highly hydrophilic while 1-ns shows poorer hydrophilicity compared with 1. The double-sided hydrophobic surfaces of 1-ns allowed the oil (dichloromethane) but protected water to pass through, being good candidate for oil/water separation. Electrochemical measurement revealed that the 2D metal–organic nanosheet 1-ns possesses modified glassy carbon electrode (1-ns/GCE) much better electron transfer ability compared with the 3D pillared-layer framework 1 modified glassy carbon electrode (1/GCE), and thus improves the electrochemical performance and sensitivity.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"16 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777075","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}

{"title":"Selective Hydroxylation of Benzene to Phenol via CuII(μ-O•)CuII intermediate by a Nonsymmetric Dicopper Catalyst","authors":"Qinqin Hu, Qi-Fa Chen, Hongtao Zhang, Jia-Yi Chen, Rong-Zhen Liao, Ming-Tian Zhang","doi":"10.1039/d4dt02872d","DOIUrl":"https://doi.org/10.1039/d4dt02872d","url":null,"abstract":"The one-step oxidation of benzene to phenol represents a significant and promising advancement in modern industries focused on the production of high-value-added chemical products. Nevertheless, challenges persist in achieving sufficient catalytic selectivity and preventing over-oxidation. Inspired by copper enzymes, we present a nonsymmetric diopper complex ([CuII2(TPMAN)(μ-OH)(H2O)]3+, 1) for the selective oxidation of benzene to phenol. Utilizing H2O2 as the oxidant, complex 1 demonstrates remarkable catalytic activity (TON of 14000 within 29 hours) and selectivity exceeding 97%, comparable to the finest homogeneous catalyst derived from first-row transition metals. Noteworthy, the significant substitute effect, alongside a negligible kinetic isotope effect (KIE = 1.05), radical trapping experiments, as well as the inconsistent standard selectivity test of •OH radical, all disapprove the conventional Fenton mechanism and rebound pathway. Theoretical investigations indicate that the active CuII(μ-O•)CuII-OH species generated through the cleavage of the O-O bond in the CuII(μ-1,1-OOH)CuI intermediate, facilitates the hydroxylation of benzene via an electrophilic attack mechanism. The nonsymmetric coordination geometry is crucial in activating the H2O2 and in the process of O-O bond cleavage.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"47 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777079","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}