Dalton Transactions最新文献

{"title":"Study of multimodal light emissions from Pr3+/Yb3+ doped NaLa(MoO4)2 phosphors for optoelectronic devices and plant-growth applications","authors":"Sonali Tomar, Neeraj Kumar Mishra, Vaibhav Chauhan, Kaushal Kumar, C. Shivakumara","doi":"10.1039/d4dt02532f","DOIUrl":"https://doi.org/10.1039/d4dt02532f","url":null,"abstract":"Recent advancements in materials design have driven the scientific community to explore phosphor materials for multifunctional applications. This study presents the multimodal light emission (downshifting – DS, quantum cutting – QC, and upconversion – UC) from Pr<small>³⁺</small>/Yb<small>³⁺</small> activated NaLa(MoO<small>₄</small>)<small>₂</small> phosphors for multifunctional applications. Under blue (449 nm) and NIR (980 nm) excitation, co-doped phosphors emit visible light through DS and UC processes caused by different f–f transitions of Pr<small>³⁺</small> ions. Additionally, when the co-doped samples are excited with blue light, they emit a near-infrared (NIR) light band ranging from 900 to 1050 nm. This is caused by the f–f transition of Yb<small>³⁺</small> resulting from energy transfer from a single Pr<small>³⁺</small> ion to a pair of Yb<small>³⁺</small> ions through the QC process. Concurrently, in-depth investigations were conducted to understand the concentration and thermal quenching mechanism. Firstly, the applicability of phosphors in optical thermometry using the luminescence intensity ratio (LIR) technique was explored, with the maximum relative sensitivity of 0.41% K<small>⁻¹</small> (448 K). A phosphor-coated LED (pc-LED) was constructed by coupling NaLa<small>_0.97</small>Pr<small>_0.03</small>(MoO<small>₄</small>)<small>₂</small> with a blue LED chip (InGaN). Furthermore, based on the observed optical properties of the prepared phosphor, its application in improving the photovoltaic performance of solar cells and indoor plant applications is systematically discussed.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"31 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848942","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":"Shape-responsive host-guest chemistry: metal-free tetra cationic porphyrin nonplanarity promoted by clay mineral interactions assessed by theoretical simulations","authors":"Eduardo Diaz Suarez, Filipe Camargo Dalmatti Alves Lima, Arles Victor Gil Rebaza, Vera R. Leopoldo Constantino, Helena Maria Petrilli","doi":"10.1039/d4dt03437f","DOIUrl":"https://doi.org/10.1039/d4dt03437f","url":null,"abstract":"Distortions in the porphyrin core from planarity can trigger a unique structure-property relationship, imparting its basicity, chemical stability, redox potential, and excited-state energetics, among other properties. The colour change promoted by such distortion is signed by redshifts in their electronic absorption spectra. The adsorption of guest meso-substituted free base porphyrins species on inorganic hosts such as clay minerals (layered aluminium or magnesium silicates) promotes colour changes, whose origin is not consensus. In this work, an extensive theoretical study was reported based on the Density Functional Theory (DFT) to model the interactions between tetracationic porphyrins comprising the meso-substituted groups N-methyl-4-pyridyl (p-TMPyP) and N-methyl-3-pyridyl (m-TMPyP), and montmorillonite (MMT) of the ideal formula [(Al1.67Mg0.33)Si4O10(OH)2]-0.33. The following conditions were evaluated: (i) p-TMPyP adsorbed or intercalated into MMT host structure, (ii) m-TMPyP intercalated into MMT; (iii) water effects in the intercalation process. The electrostatic interaction between the porphyrin and the MMT siloxane surface leads to a change in the conformation of p-TMPyP, comprising a rotation of substituent in the periphery of the macrocycle ring and a twist of the porphyrin plane. The nonplanarity of the intercalated p-TMPyP guest produces enough robust Bronsted basic sites to abstract H+ ions from intercalated water molecules, giving a dication. The macrocycle distortion can decrease the -conjugation, enhancing the localisation of the lone pair in the imine nitrogen atom. On the other hand, m-TMPyP shows slight deformations of the core macrocycle and minor changes in the dihedral angles of the meso-substituent group compared to its isomer and no protonation reaction when intercalated. Hence, the clay microenvironment is an exciting approach to induce alterations in the conformations of porphyrins, bringing about nonplanarity, and an example of a shape-responsive system based on guest-host chemistry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"59 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142848900","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":"Rational side-by-side self-assembly of gold nanorods with short and medium aspect ratios via self-evaporation method to boost their potential as surface-enhanced Raman scattering (SERS) substrate","authors":"Khương Quoc Võ, Thanh-Tuyen Thi Huynh, Anh Thu Nguyen, Trung Truong Tan","doi":"10.1039/d4dt03259d","DOIUrl":"https://doi.org/10.1039/d4dt03259d","url":null,"abstract":"Surface-enhanced Raman scattering (SERS) represents a compelling detection methodology centered on the electromagnetic fields, commonly termed \"hot spots\", generated around noble nanoparticles. Nonetheless, the efficacy of electromagnetic field (EMF) amplification is constrained when utilizing individual nanoparticles. There has been a notable lack of experimental and theoretically simulated studies regarding the increase of the electromagnetic field when gold nanorods with different aspect ratios undergo self-assembly in either perpendicular or parallel orientations to substrates. This research presents a novel and facile methodology for fabricating SERS nanosubstrates. This method entails self-assembling gold nanorods (AuNRs) with short and medium aspect ratios (AR) through natural evaporation. By manipulating the water-to-ethanol ratios, we ascertain the appropriate conditions for the rational alignment of the nanorods in both perpendicular and parallel orientations relative to the silicon substrate. These nanosubstrates have been experimentally evaluated for their ability to improve the Surface-Enhanced Raman Scattering (SERS) performance, presenting a novel perspective in this field. In addition, a computational analysis employing the finite-difference time-domain (FDTD) method was conducted to elucidate the electromagnetic field generated by nanoarrays when subjected to incident light of varying wavelengths, including 532 nm, 638 nm, and 785 nm. Notably, the FDTD simulation outcomes indicated that gold nanorods (AuNRs) possessing an aspect ratio of 3.0 and nanogaps of 2.0 nm exhibited exceptional electromagnetic field characteristics when aligned parallel to the substrate under 532 nm laser illumination. Conversely, when the AuNRs were oriented perpendicular to the substrates, they produced lower EMFs when interacting with the excited laser light. These findings can potentially contribute to the advancement of SERS nanosubstrate design.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"56 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841702","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":"Construction of ternary heterojunction photocatalyst Cu2Cl(OH)3/In/In2O3 for boosted photocatalytic CO2 reduction performance","authors":"Jiayang Huang, Yao Su, Zhangjie Qian, Miaoer Wu, Yunchang Xie, Chao Zeng","doi":"10.1039/d4dt03090g","DOIUrl":"https://doi.org/10.1039/d4dt03090g","url":null,"abstract":"The photocatalytic conversion of CO2 and H2O into useful chemicals or fuels over semiconductor photocatalysts is regarded as a promise technology to settle the problems of global warming and energy exhaustion. Whereas, the inefficient photo-absorption and slow charge dynamics limit the CO2 photoreduction efficiency. Here, a ternary heterojunction photocatalyst Cu2Cl(OH)3/In/In2O3 (Cu H IO) with intimate interface is obtained via hydrogen chemical reduction approach followed by hydrolysis reaction, where In species can be produced on the surface of In2O3 from the hydrogen chemical reaction with the calcining temperature over 500℃. The Cu H IO exhibits enhanced photocatalytic activity of CO2 conversion to the pristine In2O3, In2O3 with In species (H IO), and Cu2Cl(OH)3/In2O3 (Cu IO). On the absence of sacrificial agent or cocatalyst, the yield rate of CO and CH¬4 over Cu H IO are 4.36 and 1.09 μmol·g-1·h-1, which is 8.38-fold and 18-fold that of pristine In2O3 (0.52 and 0.06 μmol·g-1·h-1), respectively. The photocatalytic performance enhancement of Cu H IO results from the construction of the ternary heterojunction, which synchronous improve the photo-response and charge separation of In2O3. Moreover, the possible CO2 reduction pathway over Cu H IO has also been investigated and proposed. This work provides an important strategy for developing high-efficiency heterojunction photocatalyst system for solar fuel generation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841714","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":"Two-fold proton coupled electron transfer of a Ta(V) aniline complex mediated by a redox active NNN pincer ligand","authors":"Sotirios Pavlidis, Jasmin Alasadi, Amanda Opis Basilio, Josh Abbenseth","doi":"10.1039/d4dt03281k","DOIUrl":"https://doi.org/10.1039/d4dt03281k","url":null,"abstract":"We report the proton-coupled electron transfer (PCET) reactivity of an octahedral Ta(V) aniline complex supported by an acridane-derived redox-active NNN pincer ligand. The reversible binding of aniline to a Ta(V) dichloride induces significant coordination-induced bond weakening (CIBW) of the aniline N–H bonds. This enables a rare two-fold hydrogen atom abstraction, resulting in a terminal imido complex and a two-electron oxidation of the NNN pincer ligand, all while maintaining the metal's oxidation state. The bond dissociation free energies (BDFEs) of the aniline and a transient radical amido complex are estimated through stoichiometric reactions with different hydrogen atom abstractors and donors, further supported by density functional theory calculations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"145 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841703","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":"Necrosis Inducing Tetranuclear Ru(II) - Re(I) Metal Complex for Anticancer Therapy","authors":"Julia Schleisiek, Eleni Michaltsis, Stephan Mayer, Nicolas Montesdeoca, Johannes Karges","doi":"10.1039/d4dt02992e","DOIUrl":"https://doi.org/10.1039/d4dt02992e","url":null,"abstract":"Chemotherapy is one of the most widely used anticancer treatments worldwide. However, despite its clinical effectiveness, most chemotherapeutic agents are associated with severe side effects. To address this limitation, there is an urgent need for the development of novel anticancer agents. Among the promising alternatives, Ruthenium and Rhenium complexes have garnered significant attention in the scientific literature. This study proposes combining these two metal moieties into a single tetranuclear complex, bridged by a 2,2'-bipyrimidine ligand. Cytotoxicity tests revealed broad activity of the novel metal complex against multiple cancer cell lines. Mechanistic studies suggested that the complex induces cell death by necrosis. Further analyses demonstrated its ability to eradicate colon carcinoma tumor spheroids at micromolar concentrations. To the best of our knowledge, this represents the first example of a Ru(II)-Re(I) tetranuclear metal complex as an anticancer agent.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"34 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841707","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":"Rationally designed Cu(II) Schiff base metal complex anchored on NiFe2O4@Chitosan: An efficient heterogeneous and magnetically retrievable hybrid nanocatalyst for the one-pot multi-component synthesis of bioactive 1-amidoalkyl-2-naphthols","authors":"Sneha Paul, Pranjit Barman","doi":"10.1039/d4dt03009e","DOIUrl":"https://doi.org/10.1039/d4dt03009e","url":null,"abstract":"We reported, herein, the fabrication of Cu(II) Schiff base metal complex, immobilized on chitosan surface coated on NiFe2O4 MNPs, intended as a novel heterogeneous and magnetically recyclable nanocatalyst, NiFe2O4@CS@CuSB. The synthesis process starts with the preparation of NiFe2O4 MNPs, followed by coating with chitosan and then subsequent immobilization of the Cu(II) Schiff base metal complex on its surface. Through comprehensive characterization of the prepared nanocatalyst using FT-IR, PXRD, SEM, EDS, TEM, SAED, VSM, BET, XPS, and ICP-AES, the structure, surface morphology, elemental composition, and characteristics of the catalyst are revealed. For the evaluation of its catalytic activity, NiFe2O4@CS@CuSB has been utilized as a potential nanocatalyst for the one-pot multicomponent organic synthesis of 1-amidoalkyl-2-naphthol scaffolds. A straightforward, effective, one-pot, and environmentally safe synthesis of 1-amidoalkyl-2-naphthol has been accomplished using a broad range of aldehydes, 2-naphthol, urea, or amide, demonstrating the catalyst's strong resistance to different functionalities. High yields of the intended products have been obtained without the formation of byproducts. A hot filtration test was employed to evaluate the heterogeneity of the solid nanocatalyst. With potential uses in medicinal chemistry, this novel catalyst presents a viable method for the effective production of bioactive molecules.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"28 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142841705","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 sulfur-templated Ni–Ni′ coordination polymer that relies on a polarizable nickel nitrosyl hub","authors":"Manish Jana, Michael B. Hall, Marcetta Y. Darensbourg","doi":"10.1039/d4dt03174a","DOIUrl":"https://doi.org/10.1039/d4dt03174a","url":null,"abstract":"The templating properties of a diaza-nickel-<em>cis</em>-dithiolate towards triphenylphosphine gold(<small>I</small>), yielding a <em>transoid</em> [Ni(N<small>₂</small>S<small>₂</small>)·2Au(PPh<small>₃</small>)] complex (T. A. Pinder, S. K. Montalvo, A. M. Lunsford, C.-H. Hsieh, J. H. Reibenspies and M. Y. Darensbourg, <em>Dalton Trans.</em>, 2014, <strong>43</strong>, 138–144) suggested that a suitable analogue of d<small>¹⁰</small>-Au(<small>I</small>), <em>i.e.</em>, {Ni(NO)}<small>¹⁰</small>, could generate a tetrahedral nickel node for a [Ni(N<small>₂</small>S<small>₂</small>)·2Ni(NO)(X)]<small>_<em>n</em></small> coordination polymer. Monomeric precursors, derived from Feltham's [(Ph<small>₃</small>P)<small>₂</small>Ni(NO)(Cl)] (R. D. Feltham, <em>Inorg. Chem.</em>, 1964, <strong>3</strong>, 116–119) produced the bidentate/sulfur-chelated [Ni(N<small>₂</small>S<small>₂</small>)·Ni(NO)(X)] species with loss of PPh<small>₃</small>. Exchange of Cl<small>⁻</small> by azide, N<small>₃</small><small>⁻</small>, in the {Ni(NO)}<small>¹⁰</small> synthon led to the balance of electrophilicity at Ni(NO) and non-covalent (H-bonding and van der Waals) interactions that stabilized the extended chain of bridging sulfurs, in transoid connectivities, between a square planar Ni<small>^II</small> and a tetrahedral Ni, the latter within the electronic and spin-delocalized {Ni(NO)}<small>¹⁰</small> system. This study defines a new path that creates coordination polymers using metallodithiolates, the success of which, in this case, depends on the highly polarizable {Ni(NO)}<small>¹⁰</small> unit.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832071","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":"Ring-opening polymerization of ε-caprolactone with a macrocyclic tetracarbene indium complex","authors":"Henry R. Brothers, Raju Chambenahalli, Gary S. Nichol, Jennifer A. Garden, David M. Jenkins","doi":"10.1039/d4dt03198a","DOIUrl":"https://doi.org/10.1039/d4dt03198a","url":null,"abstract":"The first chiral tetracarbene indium(<small>III</small>) complexes have been synthesized by employing a rigid dianionic macrocyclic tetra-NHC ligand. The macrocyclic indium tetra-NHC bromide and ethoxide complexes are structurally similar to analagous salen complexes. The indium ethoxide complex effectively promotes living ring-opening polymerization of ε-caprolactone at room temperature.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"30 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832074","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":"Fabrication of 2D/2D Bi2MoO6/Sx@g-C3N(4-y) type-II heterojunction photocatalyst for enhanced visible-light-mediated degradation of tetracycline in wastewater","authors":"Soorya K K, Adarsh Singh, Suneel K Srivastava, Animesh Bhattacharya, Amit Bhatnagar, Ashok Kumar Gupta","doi":"10.1039/d4dt02334j","DOIUrl":"https://doi.org/10.1039/d4dt02334j","url":null,"abstract":"Aquatic biota and human health are seriously threatened by the dramatic rise in antibiotics in environmental matrices. In this regard, the present study aims to improve knowledge of the combined effects of heterojunction design and defect engineering on the photocatalytic degradation of pharmaceuticals in aqueous matrices. Advantageously, the positioning of the valence band (VB) and conduction band (CB) levels of Sx@g-C3N(4-y), being higher than those of Bi2MoO6, demonstrates the feasibility of forming a type-II heterojunction between these materials. Initially, S and N defects were inserted in S-doped g-C3N4 through an alkali-assisted calcination method (referred to as Sx@g-C3N(4-y)), as affirmed by the reduced concentrations of S and N in the end product. Thereafter, the Bi2MoO6/Sx@g-C3N(4-y) photocatalysts (referred to as BSxNy) were synthesized via a solvothermal method followed by calcination. Among the prepared samples, the integration of 10% Sx@g-C3N(4-y) with Bi2MoO6 (referred to as BSxNy (II)) demonstrated superior photocatalytic performance. Under optimal conditions, BSxNy (II) achieved a remarkable 92.4% degradation efficiency of tetracycline (TCL) in an aqueous solution after 60 min. The degradation rate of BSxNy (II) transcended that of pristine Sx@g-C3N(4-y) and Bi2MoO6 by 4.86 and 3.41 times, respectively. The higher number of active sites and the greater electron-hole pair separation are responsible for this improvement in the rate of TCL degradation. The photocatalyst also exhibited remarkable thermal/chemical stability and possessed reusability, as noted by 84% TCL degradation TCL up to 5 cycles. The radical scavenging experiment indicated \"O\" _\"2\" ^\"•-\" as the primary contributor towards TCL degradation, with h+ and •OH playing a secondary role. Additionally, a seed germination experiment used to measure phytotoxicity determined that the treated effluent was non-phytotoxic, making it suitable for irrigation.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832070","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}