Dalton Transactions最新文献_第2页

Coordinated assembly of alkali and alkaline earth metals with perfluorinated [AlF6] group to design deep-ultraviolet zero-order waveplate materials

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-31 DOI: 10.1039/d5dt00356c

Shaohua Liu, Li-Li Zhang, Ke Li, Xiaotian Ma, Xifa Long, Yun Yang

{"title":"Coordinated assembly of alkali and alkaline earth metals with perfluorinated [AlF6] group to design deep-ultraviolet zero-order waveplate materials","authors":"Shaohua Liu, Li-Li Zhang, Ke Li, Xiaotian Ma, Xifa Long, Yun Yang","doi":"10.1039/d5dt00356c","DOIUrl":"https://doi.org/10.1039/d5dt00356c","url":null,"abstract":"The capability of zero-order waveplates to manipulate the polarization of fundamental-frequency light has garnered significant attention in light of the rapid advancements in laser technology. In particular, zero-order waveplate materials in the deep-ultraviolet range (DUV; λ < 200 nm) are in urgent and short supply. In this study, three aluminum fluorides, AlF3 (P6/mmm), BaAlF5 (I4/m), and Li2KAl2F9 (C2/m), have been successfully designed and synthesized through a strategy that combines perfluorinated [AlF6] group with alkali and alkaline-earth metals. The results of experimental and theoretical calculations indicate that all three new aluminum fluorides have a short cutoff edge (λ < 200 nm) and small birefringence (0.0006 ~ 0.0056 @1064 nm). Theoretical calculations indicate that AlF3 (P6/mmm) has the shortest wavelength of 125 nm, which is comparable to the shortest wavelength of the commercially available MgF2. However, its birefringence of 0.0006 @1064 nm is about 20 times lower than that of the MgF2 (0.012 @546 nm), making it highly advantageous for fabricating deep-ultraviolet zero-order waveplate materials. Further microscopic analysis reveals that the [AlF6] group exhibits a substantial band gap of 9.17 eV and small polarizability anisotropy, indicating that the aluminum fluorides are potential candidates for designing suitable compounds for DUV zero-order waveplate materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"11 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736780","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

Novel high-efficiency and superior thermal stability red-emitting phosphor for WLED

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-31 DOI: 10.1039/d5dt00079c

Liang Zhang, Yuwen Huang, Baiqi Shao

引用次数: 0

Development of six-membered saturated cyclic diaminocarbene in main-group chemistry

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-31 DOI: 10.1039/d5dt00648a

Gargi Kundu, Sakya Singha Sen

{"title":"Development of six-membered saturated cyclic diaminocarbene in main-group chemistry","authors":"Gargi Kundu, Sakya Singha Sen","doi":"10.1039/d5dt00648a","DOIUrl":"https://doi.org/10.1039/d5dt00648a","url":null,"abstract":"In recent years, there has been a remarkable surge in the utilization of saturated N-heterocyclic carbenes (NHCs) as ligands in main group chemistry. While the field has predominantly focused on five-membered NHCs and cyclic alkyl(amino)carbene (CAAC) ligands, the investigation of six-membered NHCs (6-NHC) has only just begun. Despite possessing higher nucleophilicity than their five-membered counterparts, 6-NHCs have been less explored due to their lack of structural rigidity. This feature article aims to highlight recent developments of 6-NHCs in only main group chemistry. Exciting new studies have demonstrated the clean activation of B-H bonds in HBpin, ring expansion from a six-membered to a seven-membered ring at ambient conditions, and the stabilization of transient units \"H-B=O\" and \"(OH)B=O,\" among other intriguing phenomena. A major focus of this review is on synthetic approaches to 6-NHC-stabilized main-group compounds, and their unusual properties, as revealed through spectroscopic and crystallographic data. While the chemistry of 6-NHC is still in its nascent stage, the findings presented in this feature article underscore the need for its exploration and further investigation. Furthermore, this review provides valuable insights into meaningful synthetic methods for creating new 6-NHC·main group (B, Al, Si, P, Zn, etc.) complexes, along with mechanistic explanations for some of these reactions. These advances hold great promise for the future development of this exciting and rapidly evolving field of N-heterocyclic chemistry.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"87 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736785","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

Dual magnetic behavior of Fe(III)-dioxolene complex with tri-substituted catechol

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-31 DOI: 10.1039/d5dt00437c

Maxim Chegerev, Oleg Demidov, Stanislav Petrovich Kubrin, Pavel Nikolaevich Vasilyev, N. N. Efimov, Lingtai Yue, Maxim V. Arsenyev, Alexandr Vladimirovich Piskunov, Alyona A. Starikova

{"title":"Dual magnetic behavior of Fe(III)-dioxolene complex with tri-substituted catechol","authors":"Maxim Chegerev, Oleg Demidov, Stanislav Petrovich Kubrin, Pavel Nikolaevich Vasilyev, N. N. Efimov, Lingtai Yue, Maxim V. Arsenyev, Alexandr Vladimirovich Piskunov, Alyona A. Starikova","doi":"10.1039/d5dt00437c","DOIUrl":"https://doi.org/10.1039/d5dt00437c","url":null,"abstract":"Magnetically bistable compounds attract considerable attention due to their possible applications in molecular electronics and spintronics devices. Of special interest are spin-crossover (SCO) systems that can interconvert between the low-spin and high-spin states leading to switching the magnetic properties. Synthesis and comprehensive characterization of a family of ionic ferric-dioxolene complexes [(TPA)Fe(HO-DBCat)]ClO4 (1), [(TPA)Fe(NO2-DBCat)]ClO4 (2) and [(TPA)Fe(MeOCH2-DBCat)]ClO4 (3) (TPA = tris(2-pyridylmethyl)amine; HO-DBCat = dianion of 4,6-di-tert-butyl-1,2,3-trihydroxybenzene, NO2-DBCat = dianion of 4,6-di-tert-butyl-3-nitro-1,2-dihydroxybenzene and MeOCH2-DBCat = dianion of 4,6-di-tert-butyl-3-methoxymethyl-1,2-dihydroxybenzene) are reported. Variable temperature structural, magnetic and spectral analysis revealed that compounds 1–3 undergo a thermally induced SCO in the solid state between the high-spin (S = 5/2) and low-spin (S = 1/2) states. Alternating current magnetic susceptibility measurements indicated that the nitro-substituted complex 2 shows a field supported slow magnetic relaxation in the low-spin state at 5000 Oe. Such duality of magnetic properties makes complex 2 the first ferric compound which demonstrates a complete S = 5/2 → S = 1/2 SCO with a single molecule magnet behavior (SMM, S = 1/2). Electronic structures and magnetic properties of 1, 2 and 3 were investigated with the aid of DFT and SA-CASSCF/NEVPT2 calculations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"32 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736781","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

Photoinduced NO production from mononuclear {MnNO}6 complex bearing a metal-diaryldisulphide ligation

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-31 DOI: 10.1039/d5dt00165j

Yu-An Cheng, Su-Ying Chien, Peter Ping-Yu Chen, I-Jui Hsu, Chien-Ming Lee

{"title":"Photoinduced NO production from mononuclear {MnNO}6 complex bearing a metal-diaryldisulphide ligation","authors":"Yu-An Cheng, Su-Ying Chien, Peter Ping-Yu Chen, I-Jui Hsu, Chien-Ming Lee","doi":"10.1039/d5dt00165j","DOIUrl":"https://doi.org/10.1039/d5dt00165j","url":null,"abstract":"A solution of six-coordinate [Mn(PS2)2] (1) is inert towards nitric oxide (NO) at room temperature. In the presence of a proton source such as p-toluenesulfonic acid or perchloric acid, however, the treatment of 1 with NO in the dark leads to the formation of {MnNO}6 [Mn(NO)(SPS−SPS)] (2) with a metal–diaryldisulphide ligand, as confirmed by several spectroscopy investigations, including single-crystal X-ray diffraction. A possible pathway for the formation of 2 is determined through theoretical studies and involves the following: (i) the thiolato sulphur in 1 interacts with H+ to generate an intermediate [Mn(PS2)(PS2H)] + (A) with a S···H interaction; (ii) the reaction of A with NO yields HNO and a Mn(IV)-bound-thiyl radical species (B); and (iii) the nucleophilicity of the thiyl radical of B to an adjacent thiolato sulphur produces a five-coordinate Mn(III)–diaryldisulphide species (C), which reacts with the generated HNO to yield 2. Complex 2 is sensitive to visible light. When photolysis of 2 in solution is performed, complex 1 is regenerated and NO is released, which is related to metal–disulphide/metal–thiolate interconversion","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"58 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736787","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

Bulkiness effect dependent photosalient behaviours of photoactive cadmium coordination polymers

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-28 DOI: 10.1039/d5dt00208g

Qing-Shu Dong, Ning Wang, David James Young, Fei-Long Hu, Yan Mi

{"title":"Bulkiness effect dependent photosalient behaviours of photoactive cadmium coordination polymers","authors":"Qing-Shu Dong, Ning Wang, David James Young, Fei-Long Hu, Yan Mi","doi":"10.1039/d5dt00208g","DOIUrl":"https://doi.org/10.1039/d5dt00208g","url":null,"abstract":"Three structurally related cadmium coordination polymers CP1–CP3 {[Cd3(Pebpeb)2(L1)6] (CP1), [Cd3(Pebpeb)2(L2)6] (CP2) and [Cd6(Pebpeb)4(L3)12]·HL3 (CP3)} were constructed from the photoactive alkene ligand Pebpeb (Pebpeb = 4,4′-((1E,1′E)-(5-(pyridin-3-ylethynyl)-1,3-phenylene)bis(ethene-2,1-diyl))dipyridine; HL1 = 3-chlorobenzoic acid; HL2 = 3-nitrobenzoic acid; HL3 = 3-isopropyl benzoic acid) and Cd(II) ions in the presence of different auxiliary carboxylic acids. Different conformations of the functional olefinic ligand Pebpeb were observed in CP1–CP3 despite their similar 1D chain motif. [2 + 2] Solid-state photodimerization occurred when crystals of CP1–CP3 were irradiated with UV light (365 nm) and each displayed different photosalient (PS) responses attributed to the different bulkiness of the auxiliary carboxylic acids employed. A simple photoactuating device was prepared using a CP1-PVA (PVA = Polyvinyl Alcohol) composite.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"72 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723250","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 Methods for the Undecachlorination of [HCB11H11]- and Syntheses of [XCB11¬Cl11]- from [HCB11¬Cl11]- (X = Cl, Br, I, NH2)

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-28 DOI: 10.1039/d4dt03033h

Jack P. Raker, Jovanny J. Contreras, S. Olivia Gunther, Oleg V. Ozerov

引用次数: 0

Enhancing the hydrogen evolution activity of diiron molecular electrocatalyst by modulating substituent effect of carbon nanotubes

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-28 DOI: 10.1039/d5dt00138b

Pei-Hua Zhao, Shao-Jie Wang, Fan-Zeng Wei, Xue Su, Hui Gao

{"title":"Enhancing the hydrogen evolution activity of diiron molecular electrocatalyst by modulating substituent effect of carbon nanotubes","authors":"Pei-Hua Zhao, Shao-Jie Wang, Fan-Zeng Wei, Xue Su, Hui Gao","doi":"10.1039/d5dt00138b","DOIUrl":"https://doi.org/10.1039/d5dt00138b","url":null,"abstract":"Designing molecular catalysts to enhance hydrogen evolution activity presents both great significance and challenges. In hydrogenases, the redox group (i.e., [4Fe4S] subcluster) near catalytic active center (i.e., [2Fe2S] subcluster) plays a crucial role in modulating the enzyme's activity. Inspired by this biological strategy, three carbon-nanotube-supported diiron dithiolato hybrids, which are labeled as CNT-X-ADT (X = N, C, O), were designed. The activity of diiron catalytic center was regulated through side chain substituents (i.e., substituent effects) of CNT. Notably, a bioinspired diiron molecular compound {(μ-SCH₂)₂N(CH₂CO₂C₆H₄CHO-p)}Fe₂(CO)₆ (1), which was used to mimic diiron catalytic active center of hydrogenase enzyme, was first synthesized and then covalently attached to carbon nanotubes to form three target hybrids CNT-X-ADT (X = N, C, O). The side chain substituents, designed to mimic the activity control group, were linked to CNTs through an amination reaction. Significantly, the hydrogen evolution reaction (HER) properties of the CNT-X-ADT hybrids were systematically investigated and compared using various electrochemical techniques. Compared with CNT-C-ADT that lacks side chain regulatory ability, the average turnover frequency (TOFH₂) of CNT-N-ADT is nearly twice and gets 0.175 s⁻¹ after 5-h electrolysis, and the corresponding turnover number (TONH₂) for H₂ generation reaches 3.1 x 10³. In contrast, the CNT-O-ADT hybrid, due to its electron-withdrawing alkoxy side chain, reduces the electron density of the catalytic center, resulting in the poorest HER performance. Overall, this activity modulation by different side-chain substituents holds great significance for the development and design of metal molecular catalysts.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"57 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723378","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 of Pyridine-Functionalized Cyclic Aromatic Triamide and Formation of Copper Coordination Polymeric Complexes

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-28 DOI: 10.1039/d5dt00369e

Koji Takagi, Taiga Shirai, Daiki Miyamoto, Takuya Nakashima, Tomoyuki Ikai, Yutaka Ie, Takanori Fukushima

引用次数: 0

Copper(II) complexes with (E)–4–(2–(pyridin–2–ylmethylene)hydrazinyl)quinazoline and non–steroidal anti–inflammatory drugs: Structure and biological evaluation

IF 4 3区化学

Dalton Transactions Pub Date : 2025-03-28 DOI: 10.1039/d5dt00435g

Chrisoula Kakoulidou, Antonios Hatzidimitriou, George L Psomas

{"title":"Copper(II) complexes with (E)–4–(2–(pyridin–2–ylmethylene)hydrazinyl)quinazoline and non–steroidal anti–inflammatory drugs: Structure and biological evaluation","authors":"Chrisoula Kakoulidou, Antonios Hatzidimitriou, George L Psomas","doi":"10.1039/d5dt00435g","DOIUrl":"https://doi.org/10.1039/d5dt00435g","url":null,"abstract":"Four novel Cu(II) mixed−ligands complexes containing the quinazoline (E)−4−(2−((pyridin−2−yl)methylene)hydrazinyl)quinazoline (HL) or its methoxylated derivative (HL1) and a non−steroidal anti−inflammatory drug (mefenamic acid, flufenamic acid, diflunisal or diclofenac) as ligands were synthesized and characterized with single−crystal X−ray crystallography. In these complexes, the quinazolines are as tridentate or bridging tetradentate ligands. The studied biological properties of the complexes included the interaction with calf−thymus DNA, the ability to cleave supercoiled circular pBR322 plasmid DNA in the absence or presence of various irradiation wavelengths, the ability to reduce H2O2 or to scavenge free radicals such as 1,1−diphenyl−picrylhydrazyl and 2,2'−azinobis−(3−ethylbenzothiazoline−6−sulfonic acid), and the affinity for bovine serum albumin. The compounds can bind tightly to calf−thymus DNA via intercalation, and most of them induce notable (photo)cleavage of plasmid DNA. They can also bind tightly and reversibly to the albumin and exhibit moderate−to−significant activity towards 2,2'−azinobis−(3−ethylbenzothiazoline−6−sulfonic acid) radicals and H2O2.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"57 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723248","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