Dalton Transactions最新文献

{"title":"Inorganic organic hybrids of phosphotungstate Keggin anion and a Schiff base cation","authors":"Neeraj Kumar Mishra, Rishukumar Panday, Supriya Sabbani","doi":"10.1039/d4dt03480e","DOIUrl":"https://doi.org/10.1039/d4dt03480e","url":null,"abstract":"We present two organic-inorganic hybrids [C9H9N4O]3[PW12O40]∙C9H8N4O∙4CH3OH (1) and [C9H9N4O]3[PW12O40]∙C9H8N4O (2) consisting of 4-(salicylideneamino)-1,2,4-triazole cations and Keggin type phosphotungstate anions. Compounds 1 and 2 are characterized by NMR, UV-Vis, IR spectroscopy, and single-crystal X-ray diffraction studies. The crystal structures of compounds 1 and 2 show additional organic Schiff base molecules as lattice components. The analysis of electron paramagnetic resonance (EPR) spectra of compounds 1 and 2 shows a peak at a g-value of 2.0023, characteristic of a free radical species. The attempted spin-trapping reaction of compound 2 with C9H18NO [2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)] resulted in the formation of single crystals of [C9H18NO]3 [PW12O40] (3) consisting of TEMPOnium cation and phosphotungstate anion. Finally, compound 2 has been used as a radical initiator for free radical polymerization of styrene to polystyrene.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"23 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618686","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":"Synthesis and Redox Behavior of Si–Si Dimeric 9-Methylsilafluorene","authors":"Kelsie Wentz, Andrew Molino, George Jiang, Maxime A Siegler, David John Wilson, V. Sara Thoi, Rebekka S. Klausen","doi":"10.1039/d5dt00097a","DOIUrl":"https://doi.org/10.1039/d5dt00097a","url":null,"abstract":"Lithium-halogen exchange on 2,2’-dibromo-1,1’-biphenyl followed by salt metathesis with 1,1,2,2-tetrachloro-1,2-dimethyldisilane produced the Si–Si linked dimeric 9-methylsilafluorene (1) in 45% yield. Compound 1 was characterized in the solid state via single crystal X-ray diffraction, which revealed a highly symmetric structure. The redox behavior of 1 was studied experimentally via cyclic voltammetry, where irreversible oxidation and reduction features were observed. Density functional theory was used to further study the electronic structure of 1 as well as its reduced (1•-) and oxidized (1•+) forms. A decrease in bond dissociation energies from the neutral species (+75 kcal mol-1) to the reduced species (+43 kcal mol-1) supports Si–Si bond homolysis upon reduction, which is consistent with our observed electrochemical irreversibility.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"69 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618687","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":"Axial and Helical Chirality in Multinuclear Group 13 Complexes: Pathways to Functional Optical Materials","authors":"Toshikazu Ono, Yousuke Ooyama","doi":"10.1039/d5dt00230c","DOIUrl":"https://doi.org/10.1039/d5dt00230c","url":null,"abstract":"Main-group element complexes have emerged as promising functional dyes owing to their unique photophysical properties and potential applications in sensors, luminescent devices, and photocatalysis. Among these, multinuclear main-group complexes that incorporate multiple elements within a single ligand have garnered significant attention, particularly for their ability to exhibit chirality with optical functions. Axial and helical chirality, resulting from unique coordination geometries, represent a critical frontier in the design of functional materials. These complexes enable diverse functionalities, including circular dichroism and circularly polarized luminescence. This Frontier article highlights recent advances in the synthesis of multinuclear main-group element complexes with chirality, focusing on their structural uniqueness and photochemical characteristics. Particular emphasis is placed on Group 13 element complexes, including boron(III), aluminum(III), gallium(III), and indium(III), which exhibited unique chiral properties and photophysical behaviors. Key topics include the design strategies for chiral multinuclear frameworks, their photophysical properties, and their integration into advanced functional materials.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"54 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618688","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":"Dual center luminescence characteristics and multifunctional applications of Li2Ge7O15:Cr3+ near-infrared phosphors†","authors":"Luhui Zhou, Dashuai Sun, Zeyu Lyu, Pengcheng Luo, Zheng Lu, Xiaowei Zhang, Shuai Wei and Hongpeng You","doi":"10.1039/D5DT00301F","DOIUrl":"10.1039/D5DT00301F","url":null,"abstract":"<p >Near-infrared (NIR) phosphors have been extensively studied in recent years due to their wide-ranging applications in plant growth lighting, night vision, and biomedical imaging. However, poor thermal stability has significantly limited their practical applications in many fields. This paper reports a NIR phosphor with dual emission centers, Li<small>₂</small>Ge<small>₇</small>O<small>₁₅</small>:Cr<small>³⁺</small> (LG:Cr<small>³⁺</small>). Cr1 located at [GeO<small>₆</small>] produces narrow-line emission through the spin-forbidden <small>²</small>E → <small>⁴</small>A<small>₂</small> transition, and as the temperature increases, electrons in the <small>²</small>E level thermally migrate to the <small>⁴</small>T<small>₂</small> level, resulting in emission from the <small>⁴</small>T<small>₂</small> state. In contrast, Cr2 located at [LiO<small>₆</small>] generates broadband emission through the spin-allowed <small>⁴</small>T<small>₂</small> → <small>⁴</small>A<small>₂</small> transition, but this emission disappears due to thermal quenching effects as the temperature increases, making it undetectable at room temperature. The optical thermometry applications of the LG:Cr<small>³⁺</small> phosphor were investigated using the fluorescence intensity ratio (FIR) technique, achieving a relative sensitivity (<em>S</em><small>_r</small>) of 2.77% K<small>⁻¹</small> at 100 K. Finally, a NIR phosphor-converted diode (NIR pc-LED) was fabricated using this phosphor and a 410 nm chip, demonstrating potential applications in biomedical imaging and night vision.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 14","pages":" 5739-5746"},"PeriodicalIF":3.5,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618691","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":"Exploring the complexation behavior of NpO2+ with diglycolamide in an ionic liquid vs. aqueous solution","authors":"Seraj A. Ansari, Ashutosh Srivastava, Rajesh B. Gujar, Musharaf Ali, Prasanta Kumar Mohapatra, Willem Verboom","doi":"10.1039/d5dt00027k","DOIUrl":"https://doi.org/10.1039/d5dt00027k","url":null,"abstract":"Complexation of NpO2+ with tetramethyl diglycolamide (TMDGA) was investigated in an ionic liquid (IL: 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide, Bumim.Tf2N) with an objective to understand its complexation behaviour and its optical properies in IL and aqueous media. We successfully prepared NpO2(Tf2N) salt and its complexation with TMDGA was studied by absorption spectroscopy. Similar to aqueous medium, TMDGA formed a perfectly centrosymmetric [NpO2L2]+ complex which was evident from the disappearance of the 980 nm absorption band of neptunyl cation. The formation constant (logβ) was arrived as 3.82±0.11 and 7.13±0.24 for [NpO2L]+ and [NpO2L2]+ complexes, respectively. The logβ values were several times higher in IL medium than the values found in aqueous medium (1.37±0.05 and 2.47±0.71). Our results indicated that though the NpO2+ cation forms stronger complex with TMDGA in IL medium vis-a-vis aqueous medium, the nature of the bonding and the structural conformations in both the media are identical.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"8 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143627518","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":"Six-fold Screening unfolds optimized Rylene Diimides towards Organic Solar Cell: A DFT Perspective","authors":"Sri Vanaja Swaminathan, tanay kundu, Amrita Pal","doi":"10.1039/d5dt00250h","DOIUrl":"https://doi.org/10.1039/d5dt00250h","url":null,"abstract":"Harnessing the sunlight to electricity is the most sustainable form of alternative energy. Apart from commercial silicon solar cells, organic solar cells (OSCs) have great potential due to their flexibility, processability and cost. To improve device performance, broadband absorption, electrical mobility and charge separation are the key components for optimization. Although discrete efforts have been dedicated comprehending the role of different chemical structures on their power conversion efficiencies (PCE), a systematic screening of multiple structural factors on PCE has been non-existent. Herein, we have shortlisted rylene diimides as the model acceptors in OSCs and demonstrated the role of a) expanding the rylene core (pyromellitic to bisazulene); b) changing ring size (5-member and 6-member) and positions (2,3- vs 1,8/9) of the diimide; c) changing diimide sidechain from alkyl to aryl, and d) twisting core-planarity of the rylene (pyrene to corannulene) and the effect on their structural parameters, optical absorption spectra and electron mobilities. Moreover, the combined six-fold screening predicts the candidate with highest electron mobility in the series. Such comprehensive assessment of critical factors on OSC performance will pave the way for improved design of acceptor molecules for higher PCE.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"183 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618864","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":"Amino-ionic liquids assisted highly compatible mixed matrix membrane of ZIF-8 and PIM-1 for efficient CO2/N2 separation","authors":"Zhaojie Wang, Xinle Sun, Qinglong Liu, Caifeng Xia, Qikang Yin, Siyuan Liu, Xiaoqing Lu, Hongyu Chen","doi":"10.1039/d5dt00335k","DOIUrl":"https://doi.org/10.1039/d5dt00335k","url":null,"abstract":"Mixed matrix membranes (MMMs), which incorporate metal-organic frameworks (MOFs) nanofillers within a polymer matrix, offer a highly promising solution for CO2 capture and separation. However, poor interfacial compatibility and filler aggregation in MMMs pose significant challenges to enhancing CO2/N2 separation performance. Here, we present a novel approach using amino ionic liquid modification to optimize MMMs, where the modified AFIL promotes the formation of ZIF-8 with well-defined facets and sharp edges, and enhances the compatibility between ZIF-8 particles and PIM-1 polymer matrix for favorable CO2 affinity and selective CO2 transport. The resulting 10 wt.% AFIL@ZIF-8/PIM-1 exhibits exceptional gas separation performance with a CO2 permeability of 7864262.2 Barrer and a CO2/N2 selectivity of 29.661.96. More importantly, the incorporation of AFIL into the ZIF-8 pores significantly enhances the thermal stability and aging resistance of AFIL@ZIF-8/PIM-1 MMMs via structural support and hydrogen bonding interactions. This work provides a practical approach to developing hybrid membranes for CO2/N2 separation, showcasing improved overall performance and strong interfacial compatibility.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"18 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618685","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":"RbB7O10(OH)2 and NaB11O16(OH)2: Alkali Metal Hydroxyborates with Two-dimensional Layered Structures and Large Birefringence","authors":"Yujing Zheng, Ke Li, Ling Huang, Fangfang Zhang","doi":"10.1039/d5dt00426h","DOIUrl":"https://doi.org/10.1039/d5dt00426h","url":null,"abstract":"Hydroxyborates have attracted much research attention due to their rich structural and outstanding optical properties. Herein, two new alkali metal hydroxyborates, RbB7O10(OH)2 and NaB11O16(OH)2, with two-dimensional (2D) layered structures have been synthesized in a closed system using the high-temperature solution method. UV-VIS-NIR diffuse reflectance spectrum shows that RbB7O10(OH)2 has a UV cutoff edge below 200 nm. Theoretical calculations indicate that both compounds exhibit large band gaps (7.40 and 7.41 eV) and large birefringence (0.074 and 0.105 at 1064 nm), respectively. Additionally, the origin of the birefringence in title compounds has been analyzed using the Response Electron Distribution Anisotropy (REDA) method.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"5 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608280","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":"Uranyl-based Metal-Organic Framework Featuring an Eight-connected U4L2 Cage for Guest Capture","authors":"Shuang Deng, Zhiwei Huang, Xuan Fu, Zhi-heng Zhou, Zhi-Ren Guo, Lei Mei, Jipan Yu, Yanqiu Zhu, Nannan Wang, Kongqiu Hu, Weiqun Shi","doi":"10.1039/d5dt00307e","DOIUrl":"https://doi.org/10.1039/d5dt00307e","url":null,"abstract":"A novel (3, 6)-connected uranyl-based MOF (IHEP-50) was synthesized by a judicious combination of UO22+ and polycarboxylic acid, 4,4',4'',4''',4'''',4'''''-(((1,3,5-triazine-2,4,6-triyl)tris(azanetriyl))hexakis(methylene))hexabenzoic acid (H6DTPCA). Two DTPCA6- ligands are connected together via four uranyl cations to form a lantern-shaped cage U4L2, which is further connected with other eight equivalent ones to form the 3D porous framework with two kinds of 1D channels. These large pore structures give it a certain potential for guest molecules capture. Adsorption experiments indicate that IHEP-50 can selectively-remove positively charged dyes over negatively charged and neutral ones. In addition, IHEP-50 demonstrates notably adsorption performance for gaseous iodine, achieving a maximum adsorption capacity of 253.5 mg·g-1.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"9 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600154","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":"Carbon composited zinc ion doped vanadium dioxide synthesized by the hydrothermal method based on surfactant regulation as the cathode material for aqueous zinc ion batteries","authors":"Jian Li, Xixun Shen, Yanheng Zhao, Qunjie Xu","doi":"10.1039/d5dt00084j","DOIUrl":"https://doi.org/10.1039/d5dt00084j","url":null,"abstract":"Aqueous zinc-ion batteries are regarded as having the potential for large-scale application owing to their low cost and inherent safety. However, due to the slow kinetics of cathode materials and the suboptimal microstructure, AZIBs often exhibit unsatisfactory stability during actual cycling. The rational design and development of cathode materials possessing high specific capacity and long-cycle stability hold significant importance for the progress of AZIBs. Here, carbon-nanosphere-composited, zinc-ion-doped VO2 (SZVO@C) electrode materials were fabricated through hydrothermal process with the assistance of sodium dodecyl sulfonate. Under the modulation of surfactants, the SZVO@C electrode exhibits a rose-like cluster structure composed of nanosheets, this confers a more extensive specific surface area, measuring 40.2 m² g-1. Under a current density of 0.5 A g-1, the SZVO@C electrode exhibits an outstanding specific capacity of 360 mAh g-1. Moreover, it showcases exceptional cycling stability at 5 A g-1, retaining an impressive 98% of its capacity even after 2000 cycles. The SZVO@C electrode's remarkable cycling performance can be attributed to two key factors. Firstly, it has an outstanding specific surface area. Secondly, there is a morphological alteration that occurs during the first charge. The tight bonding between the cathode material and conductive carbon improves electron transfer efficiency and effectively reduces charge transfer resistance. GITT tests show that the SZVO@C electrode has an excellent Zn2+ diffusion coefficient of 1.3 × 10-10 to 1.52 × 10-8 cm2 s-1, which provides a strong guarantee for its excellent cycling performance. The ex-situ XPS and XRD examinations unveil the storage mechanism of Zn2+. During the initial cycle, the SZVO@C electrode forms the new phase ZnxV2O5·nH2O, the pristine ZnyVO2 engages in a subsequent reversible cycle along with the new phase. This research work clearly demonstrates that employing surfactants to regulate the microstructure of cathode materials and incorporating carbon materials constitute a potent strategy to enhance the performance.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"17 1","pages":""},"PeriodicalIF":4.0,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143600152","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}