Chemistry - An Asian Journal最新文献

{"title":"N-Alkyl Chain Induced Molecular Aggregation in Mononuclear Gold(I)-N-Heterocyclic Carbene Complexes for Blue Light Emitting Applications.","authors":"Ganesan Prabusankar, Gopendra Muduli, Moulali Vaddamanu, Arruri Sathyanarayana, Kumar Siddhant, Arushi Rawat, Osamu Tsutsumi","doi":"10.1002/asia.202401356","DOIUrl":"https://doi.org/10.1002/asia.202401356","url":null,"abstract":"<p><p>We report the photoluminescence and thermal stability correlation between blue emitting mononuclear gold(I)-NHC chloride complexes, N-(9-anthracenyl)-N'(n-alkyl)imidazol-2-ylidene gold(I) chloride (alkyl = n-butyl (1), n-pentyl (2), n-hexyl (3)). The solid-state study reveals a unique molecular packing due to hydrogen bonding, aurophillic interaction, and CH···π interactions in all 1-3. In addition, the π···π stacking has been found in 1. All these complexes show good thermal stability due to the strong metal-ligand bond strength along with crystal packing. In addition, 1-3 emits a blue colour in both solution and crystalline state. The quantum yield in the crystalline state was found to be high for 1 (22.44%) compared to 2 (9.90%), and 3 (14.98%). A similar high quantum yield for blue-emitting gold(I)-NHC chloride complex is rare. This promising quantum yield for 1 can be ascribed to the crystal packing effect. The theoretical calculations were carried out to understand the electronic and structural properties of 1-3. Computational studies revealed the origin of the luminescence behaviour of complexes. The blue light emitting thin film and LED are demonstrated using 1 exhibited the emission peak at the blue region with Commission Internationale de L'Eclairage (CIE) coordinates near the National Television Standards Committee (NTSC) value.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401356"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142918785","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 Doubly meso-α Linked N-Confused Porphyrin Tape Silver(III) Complex Comprising an Antiaromatic Pyrrolo[2,3-f]indole Segment.","authors":"Akito Nakai, Osamu Iwanaga, Takayuki Tanaka, Atsuhiro Osuka","doi":"10.1002/asia.202401144","DOIUrl":"10.1002/asia.202401144","url":null,"abstract":"<p><p>The free base form of doubly meso-α linked N-confused porphyrin (NCP) tape 3 was successfully synthesized via Ir(I) mediated intramolecular coupling. The following silver complexation afforded the Ag(III) complex of doubly meso-α linked NCP tape 4. While 3 exhibited 38π aromatic characters, 4 exhibited not only 18π aromatic NCP-type characteristics but also a decent antiaromatic contribution of 12π pyrrolo[2,3-f]indole segment, as probed by NMR spectra, absorption spectra, and DFT calculations.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401144"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142360835","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":"Nano-Metal-Organic Frameworks and Nano-Covalent-Organic Frameworks: Controllable Synthesis and Applications.","authors":"Yaxun Hu, Songtao Zhang, Kun Xu, Xiaoli Zhuang, Yijian Tang, Hao Gong, Yecan Pi, Tian Tian, Huan Pang","doi":"10.1002/asia.202400896","DOIUrl":"10.1002/asia.202400896","url":null,"abstract":"<p><p>Nanoscale framework materials have attracted extensive attention due to their diverse morphology and good properties, and synthesis methods of different size structures have been reported. Therefore, the relationship between different sizes and performance has become a research hotspot. This paper reviews the controllable synthesis strategies of nano-metal-organic frameworks (nano-MOFs) and nano-covalent-organic frameworks (nano-COFs). Firstly, the synthetic evolution of nano-frame materials is summarized. Due to their special surface area, regular pores and adjustable structural functions, nano-frame materials have attracted much attention. Then the preparation methods of nanostructures with different dimensions are introduced. These synthetic strategies provide the basis for the design of novel energy storage and catalytic materials. In addition, the latest advances in the field of energy storage and catalysis are reviewed, with emphasis on the application of nano-MOFs/COFs in zinc-, lithium-, and sodium-based batteries, as well as supercapacitors.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400896"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386673","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":"Photoluminescent and Electrochemiluminescent Detection of Fe³⁺ Using Cyclometalated Iridium Complexes via Fe³⁺-Catalyzed Hydrolysis.","authors":"Hyun Seung No, Minhee Sim, Ik-Soo Shin, Joohoon Kim, Jong-In Hong","doi":"10.1002/asia.202400805","DOIUrl":"10.1002/asia.202400805","url":null,"abstract":"<p><p>Ferric ion (Fe³⁺) is a biologically abundant and important metal ion. We developed several cyclometalated iridium complex-based molecular sensors (1, ppy-1, 1-phen, 1 a, and 1_OMe) for the detection of Fe³⁺ using an acetal moiety as the reaction site. The acetal moiety in iridium complexes undergoes Fe³⁺-catalyzed hydrolysis and subsequent formation of a formyl group, resulting in turn-off photoluminescent and electrochemiluminescent responses. Sensor 1 showed excellent selectivity toward Fe³⁺ over other biologically important metal ions. Furthermore, we compared the performance of the sensors based on the structural differences of the iridium complexes, and revealed a relationship between the structure and chemical properties through electrochemical experiments and computational calculations.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400805"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142386675","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":"Glassy Carbon Electrodes Modified with Ru Nanoparticles Loaded in B-Doped Imidazolium Porous Organic Polymers for Hydrogen Evolution Reaction.","authors":"Shasha Ma, Di Chen, Jie Xu, Zhaobin Ye, Jianyong Zhang","doi":"10.1002/asia.202401042","DOIUrl":"10.1002/asia.202401042","url":null,"abstract":"<p><p>Porous organic polymers (POPs) are a type of porous material composed of organic structural units connected by covalent bonds and POPs have been used as efficient electrocatalysts for hydrogen evolution reaction (HER). Herein, glassy carbon electrode (GCE) is chemically modified by B-doped imidazolium-based porous organic polymers loaded with Ru nanoparticles on the GCE surface. The incorporation of B in the POPs regulates the electronic structure of electrocatalysts to enhance their inherent electrocatalytic activity for HER. The optimized modified electrode GCE-Ru/PIM-Br2 exhibits a low overpotential of 271 mV at a current density of 10 mA cm^-2 with a small Tafel slope (80 mV dec^-1) in acidic solutions, and shows long-term stability for up to 22 h. This work presents a strategy to develop B-doped porous electrodes with loaded metal nanoparticles to strengthen the catalytic performance of electrocatalysts.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401042"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454095","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 Structures of Oxide -Centred Alkali Metal (K, Li)/Lanthanoid (Ln3 or 4) 3,5-Dimethylpyrazolate Cages - Herbert Schumann Revisited.","authors":"Daniel Werner, Zhifang Guo, Glen B Deacon, Peter C Junk","doi":"10.1002/asia.202400964","DOIUrl":"10.1002/asia.202400964","url":null,"abstract":"<p><p>Reaction of lanthanoid tris(3,5-dimethylpyrazolate) compounds, [Ln(Me₂pz)₃(thf)]₂ (Ln=La 1 a, Ce, Pr, Dy 1 b, Yb, Lu) with potassium or lithium bistrimethylsilylamide and with or without added 3,5-dimethylpyrazole, or of lanthanoid tris(bistrimethylsilyl)amide complexes with potassium bistrimethylsilylamide and 3,5-dimethylpyrazole have yielded a variety of oxide centred Ln₃ or Ln₄/(K or Li)_1-3 multinuclear cages, namely, [La₄O(Me₂pz)₁₁ K(thf)₂] (2 a), [La₄O(Me₂pz)₁₁Li(Me₂pzH)]⋅0.5Hexane (2 b), [La₄O(Me₂pz)₁₀(Me₂pzH)] (2 c) (from heating 1 a in toluene), [Ce₃O(Me₂pz)₉K₂(dme)₂] (3 a), [Ce₃O(Me₂pz)₉Li₂(thf)₂]⋅0.5Hexane (3 b) and [Ce(Me₂pz)₅Li₂(thf)₃] (3 c), which crystallized together, [Ce₃O(Me₂pz)₁₀K₃(thf)₃] (3 d), [Pr₃O(Me₂pz)₁₀K₃(thf)₃] (4), [Dy₃O(Me₂pz)₉K₂(thf)₂]⋅THF (5), [Yb₃O(Me₂pz)₉K₂(thf)₂]⋅THF (6), and [Lu₃O(Me₂pz)₉K₂(thf)₂]⋅THF (7). Crystals of {[K₈(Me₂pz)₈(thf)₂]⋅THF}_∞ (8) were also obtained from the preparation of 7. From reaction of [Ce(Me₂pz)₃(thf)]₂ with potassium tert-butoxide in toluene, the cerium(IV) heterobimetallic polymer [Ce₂(Me₂pz)₆(OtBu)₄K₂]_∞ (9) was isolated. In the Ln₃O and the Ln₄O cages, the Ln atoms have triangular and distorted tetrahedral arrangements about the central oxygen, respectively. The relationship of the alkali metals to the central oxygen varies considerably. Thus in 2 a, 2 b, there is no bonding, in 3 a, both K atoms interact weakly, in 3 b one of the two Li atom is bound, in 3 d, 4, one of three K atoms in bound, whilst in 5-7, both K atoms are bound. All metals are bound to the cages by a variety of pyrazolate binding modes, with up to five different exhibited in some structures, and a new coordination mode, μ₄-1κ(N):2κ(N'):η⁵:η⁵, was observed in two complexes. In the structure of 2 c, the coordinated Me₂pzH ligand binds to two metals through a single nitrogen, the first time this has been observed for a pyrazole donor. The complex 9 is polymeric with all metals bridged by butoxide donors as well as by Me₂pz groups.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400964"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142454097","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":"Organometallic Ru(III) Catalysts for α-Alkylation of Carbonyl Compounds using Alcohols: Mechanistic Insights via Detection of Key Intermediates.","authors":"Sain Singh, Rajat Saini, Virendra Kumar Chaudhary, Kaushik Ghosh","doi":"10.1002/asia.202400811","DOIUrl":"10.1002/asia.202400811","url":null,"abstract":"<p><p>Three novel cyclometalated ruthenium complexes ([Ru.L⁽⁹⁾] [Ru.L⁽¹⁰⁾] and [Ru.L⁽¹¹⁾]) featuring azo functionalities were synthesized and characterized using a variety of spectroscopic techniques, namely FT-IR, electronic absorption spectroscopy, and ESI-MS. Representative solid-state structures of the acquired complexes were determined through X-ray crystallography. These complexes were evidenced to be efficient catalysts for the synthesis of various α-alkylated compounds utilizing simple acetophenone derivatives with easily affordable and economically viable alcohols, which were isolated and characterized via ¹H and ¹³C NMR spectroscopy. The optimum reaction conditions were found by employing toluene as solvent and potassium tert-butoxide as a base at 115 °C temperature utilizing 0.8 mol % of catalyst [Ru.L⁽¹⁰⁾]. The yield of the desired compounds was found to be in the range of 83-97 %. Additionally, mass spectrometry provided insights into the in-situ generated ruthenium hydride and ruthenium alkoxy intermediates, shedding light on the catalytic mechanism.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400811"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556517","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 Advances in Organic Photocatalyst-Promoted Carbohydrate Synthesis and Modification under Light Irradiation.","authors":"Jing Wang, Fan Zhou, Yuping Xu, Lei Zhang","doi":"10.1002/asia.202401114","DOIUrl":"https://doi.org/10.1002/asia.202401114","url":null,"abstract":"<p><p>Photoredox catalysis has been developed as a sustainable and eco-friendly catalytic strategy, which might provide innovative solutions to solve the current synthetic challenges and barriers in carbohydrate chemistry. During the last few decades, the study of organic photocatalyst-promoted carbohydrate synthesis and modification has received significant attention, which provides an excellent and inexpensive metal-free alternative to photoredox catalysis as well as introduces a new fastest-growing era to access complex carbohydrates simply. In this review, we aim to provide an overview of organic photocatalyst-promoted carbohydrate synthesis and modification under light irradiation, which is expected to provide new directions for further investigation.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401114"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142913337","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":"Donor-Acceptor-Donor Dyads with Electron-Rich π-Extended Azahelicenes to Panchromatic Absorbing Dyes.","authors":"Satoru Hiroto, Moeko Chujo","doi":"10.1002/asia.202400830","DOIUrl":"10.1002/asia.202400830","url":null,"abstract":"<p><p>Panchromatic dyes have been highly useful in the realm of optical devices. Here, we report that panchromatic dyes with heterohelicenes have been successfully synthesized using a donor-acceptor strategy. Our synthesis resulted in the creation of π-extended aza[5]helicene oligomers with butadiyne linkages, which displayed bathochromically shifted absorption and emission spectra. The solvent-dependent optical measurements revealed the intramolecular charge transfer characteristic of these molecules, and theoretical calculations described the biased molecular orbitals on the azahelicene units that generated the charge-transfer characteristic. Encouraged by these results, we also prepared donor-acceptor-donor dyads using azahelicenes and dimide derivatives, resulting in panchromatic absorbing characteristics covering the range from 250 nm to 800 nm. Theoretical calculations showed the presence of mixed charge-transfer transitions and localized transitions on the azahelicene units, which led to a broad light-absorbing property covering the near IR region. Additionally, we conducted measurements of circular dichroism and circularly polarized luminescence for the obtained products. The g-values were reduced by oligomerization, indicating that the lowest energy transitions were allowed in nature.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400830"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102563","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":"NiIr Nanowire Assembles as an Efficient Electrocatalyst Towards Oxygen Evolution Reaction in Both Acid and Alkaline Media.","authors":"Ning Zhang, Yalun Wang, Ruxue Wu, Xianwen Yang, Yan Wu, Fangmu Wang, Ping Cui, Guigao Liu, Wei Jiang, Haijiao Xie","doi":"10.1002/asia.202400851","DOIUrl":"10.1002/asia.202400851","url":null,"abstract":"<p><p>Oxygen evolution reaction (OER) is the rate-limiting step in water electrolysis due to its sluggish kinetic, and it is challenging to develop an OER catalyst that could work efficiently in both acid and alkaline environment. Herein, NiIr nanowire assembles (NAs) with unique nanoflower morphology were prepared by a facile hydrothermal method. As a result, the NiIr NAs exhibited superior OER activity in both acid and alkaline media. Specifically, in 0.1 M HClO₄, NiIr NAs presented a superior electrocatalytic performance with a low overpotential of merely 242 mV at 10 mA cm^-2 and a Tafel slope of only 58.1 mV dec^-1, surpassing that of commercial IrO₂ and pure Ir NAs. And it achieved a significantly higher mass activity of 148.40 A/g at -1.5 V versus RHE. In 1.0 M KOH, NiIr NAs has an overpotential of 291 mV at 10 mA cm^-2 and a Tafel slope of 42.1 mV dec^-1. Such remarkable activity makes the NiIr NAs among the best of recently reported representative Ir-based OER electrocatalysts. Density functional theory (DFT) calculations confirmed alloying effect promotes surface bonding of NiIr with oxygen-containing reactants, resulting in excellent catalytic properties.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202400851"},"PeriodicalIF":3.5,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398720","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}