Journal of Chemical Sciences最新文献

{"title":"Polyoxometalate-driven assembly of inorganic–organic hybrid materials: Proton conductivity studies","authors":"Parvathy M Unnikrishnan,&nbsp;Gopika Premanand,&nbsp;Samar K Das","doi":"10.1007/s12039-024-02339-6","DOIUrl":"10.1007/s12039-024-02339-6","url":null,"abstract":"<div><p>A zinc-containing, one-dimensional coordination polymer, [Zn(NH₂trz)₃](NO₃)₂ (1D-CP, NH₂-trz <span>(=)</span> 4-amino-4H-1,2,4-triazole) has been employed to synthesize two water-insoluble proton conductors, ZnL-PW₁₂ and ZnL-SiW₁₂ (L <span>(=)</span> 4-amino-4H-1,2,4-triazole), that are formulated as {[Zn(NH₂trz)₃](NO₃)}₂{HPW₁₂O₄₀}·4H₂O and [Zn(NH₂trz)₃][NH₃trz]₂[SiW₁₂O₄₀]·10H₂O, respectively. These proton conductors were prepared through simple room-temperature aqueous reactions involving [Zn(NH₂trz)₃](NO₃)₂ and phosphotungstic or silicotungstic acids, which proceed via aqueous disassembly of the CP, followed by recrystallization into a new phase driven by the addition of heteropolyanions. Here, the Keggin POMs, specifically H₃PW₁₂O₄₀ and H₄SiW₁₂O₄₀, impart enhanced stability to the overall structures of the resulting Zn-complex-POM adducts, ZnL-PW₁₂ and ZnL-SiW₁₂. Upon mixing the aqueous solutions of 1D-CP and POMs, immediate precipitations of the water-insoluble inorganic–organic hybrid products are obtained, the aqueous suspensions of which exhibit acidic pH. This observation prompted us to investigate proton conductivity behaviour of the resulting materials. As anticipated, the isolated products, ZnL-PW₁₂ and ZnL-SiW₁₂ exhibit significant proton conductivity values of 5.1 × 10⁻³ and 5.6 × 10⁻³ S cm⁻¹, respectively, at 80°C and 98% relative humidity, demonstrating excellent stability for about 30 h with decent cycling stability over four heating–cooling cycles.</p><h3>Graphical abstract</h3><p>A zinc-based one-dimensional coordination polymer, [Zn(NH₂-trz)₃](NO₃)₂ (1D-CP), was modified into two water-insoluble proton conductors by a process involving the disassembly and subsequent restructuring of the coordination polymer into more stable inorganic–organic hybrids by the addition of phosphotungstic and silicotungstic heteropolyanions. The resulting hybrid materials, ZnL-PW₁₂ and ZnL-SiW₁₂ (L = 4-amino-4H-1,2,4-triazole), exhibit significant proton conductivities of 5.1 × 10⁻³ and 5.6 × 10⁻³ S cm⁻¹, respectively, and demonstrate excellent stability for &gt;30 h under the operational conditions.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143513411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Monoacetylated bishydroperoxide-derived singlet molecular oxygen-mediated oxidative coupling of primary and secondary alcohols with phenylhydrazine: Synthesis of 1,3,5-trisubstituted pyrazoles","authors":"Z Najminejad,&nbsp;D Azarifar,&nbsp;S-M Khatami","doi":"10.1007/s12039-024-02341-y","DOIUrl":"10.1007/s12039-024-02341-y","url":null,"abstract":"<div><p>Oxidative synthesis of pyrazoles from aromatic alcohols and phenyl hydrazine has been achieved by using trans-5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-yl ethaneperoxate and KOH. The reaction proceeds via oxidative coupling of primary and secondary alcohols with phenylhydrazines by singlet molecular oxygen produced from trans-5-hydroperoxy-3,5-dimethyl-1,2-dioxolane-3-yl ethaneperoxate at room temperature, and broad range of derivatives were obtained in good to excellent yields. Advantageous features of the present methodology include mild reaction conditions, transition metal-free, good functional-group tolerance, use of readily available primary and secondary alcohols and so on.</p><h3>Graphical abstract</h3><p>Oxidative synthesis of pyrazoles from aromatic alcohols and phenyl hydrazine has been achieved by using trans-5-hydroperoxy-3,5-dimethyl-1,2-dioxolan-3-yl ethaneperoxate/KOH. The reaction proceeds via oxidative coupling of primary and secondary alcohols with phenylhydrazines by singlet oxygen produced from trans-5-hydroperoxy-3,5-dimethyl-1,2-dioxolane-3-yl ethaneperoxate and a range of derivatives were obtained in good to excellent yields\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143496867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Computational study on non-covalent interactions in benzene–X complexes (X = He, Ne and Ar)","authors":"Achal S Bhoge,&nbsp;Sachin D Yeole","doi":"10.1007/s12039-024-02337-8","DOIUrl":"10.1007/s12039-024-02337-8","url":null,"abstract":"<div><p>Weakly bound complexes of inert gas atoms with aromatic rings have received the attention because these are important for understanding the several solution- and condensed-phase properties. Extrapolated complete basis set (CBS) limit interaction energies for van der Waal complexes of benzene with He, Ne and Ar were calculated by using MP2 level and B2PLYPD3 and M06-2X functionals, employing aug-cc-pVTZ basis set. It was observed that as the size of inert gas increases, the interaction energy becomes more negative suggesting more stabilizing interaction. In sandwich complexes, the magnitude of CBS interaction energies was found to be double when compared to benzene complexes. The calculated vibrational stretching frequencies of cationic benzene complexes show red-shift, whereas almost same frequencies are found in sandwich complexes, with respect to benzene–X (X = He, Ne and Ar) complexes. However, in deuterated benzene–X complexes, the C–D stretching frequencies show a decrease in frequency value compared to benzene–X complexes and this may due to the presence of deuterated atom. Apart from that, the complexes, (benzene)⁺⁺–X dication and X–(benzene)⁺–X sandwich cation were also studied using MP2/aug-cc-PVTZ level. It is observed that the charge is increased when moving from (benzene)⁺–X to (benzene)⁺⁺–X complexes, the strength of interaction is increasing. Further, the nature of interaction present in benzene–X complexes was investigated by energy decomposition analysis using SAPT analysis. The SAPT analysis revealed that the contribution from dispersion terms is increasing when moving from He to Ar complexes.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143361946","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Simple and efficient synthesis of novel thiazolo[4,5-e]indole derivatives via three-component reaction","authors":"Bing-Wei Wang,&nbsp;Ming-Han Huang,&nbsp;Xue Wang,&nbsp;Dong-Sheng Chen","doi":"10.1007/s12039-024-02345-8","DOIUrl":"10.1007/s12039-024-02345-8","url":null,"abstract":"<div><p>A series of thiazolo[4,5-<i>e</i>]indole derivatives have been obtained by a three-component domino reaction of 2-methylbenzo[<i>d</i>]thiazol-5-amine, arylglyoxal monohydrates and cyclohexane-1,3-dione in ethanol medium at 80°C catalyzed by acetic acid. Notable features of this synthesis are mild reaction, high synthesis efficiency, simple post-treatment operation and only water is generated as a byproduct.</p><h3>Graphical abstract</h3><p>\u0000A new procedure for the synthesis of thiazolo[4,5-<i>e</i>]indole derivatives.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143110186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Amorphous microporous polymer with high-density sulphonic acid for proton conduction","authors":"Kun Zhang,&nbsp;Yanting Zhang,&nbsp;Lei Wu,&nbsp;Qingchao Liu","doi":"10.1007/s12039-024-02340-z","DOIUrl":"10.1007/s12039-024-02340-z","url":null,"abstract":"<div><p>Proton conductors play a significant role in various fields, and recent research has focused on exploring crystalline porous materials for their favourable proton-transport properties. However, synthesizing these materials often poses challenges, especially in achieving crystallinity. In this study, we have successfully developed an innovative approach by constructing an amorphous microporous polymer (AMP) structure. Unlike traditional methods that require crystallization, our AMP maintains a certain pore space, while avoiding the need for strict crystallinity. Remarkably, this newly developed AMP displays high-density sulphonic acid sites on its skeleton, enabling it to function as an efficient proton conductor across a wide range of relative humidity (RH) levels. At 70°C and 100% RH, it achieves an impressive maximum conductivity value of 3.34 × 10⁻³ S cm⁻¹. Such an excellent performance can be attributed to the low activation energy for proton conduction, measuring a mere 0.266 eV. This signifies a Grotthuss mechanism, indicating that protons readily jump along hydrogen bonds within the material.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142995362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Role of Hartree–Fock exchange in spontaneous proton transfer reactions","authors":"Arzoo,&nbsp;G. Naresh Patwari","doi":"10.1007/s12039-024-02335-w","DOIUrl":"10.1007/s12039-024-02335-w","url":null,"abstract":"<div><p>Electric field experienced by a protic group depends primarily on solvent configuration and those configurations in which the electric field along the protic group exceeds a critical value, results in spontaneous proton transfer. Electronic structure calculations using density functional theory (DFT) result in artifacts in estimating critical electric fields for the spontaneous proton transfer process, often leading to bistable behaviour, in contrast to MP2 level calculations. Discrepancies in assessing critical electric fields using the DFT method can be attributed to the under-representation of Hartree–Fock exchange in many commonly used functionals, such as B3LYP and M06-2X, whose effect is precipitative in the proton transferred structures. Using the (critical) electric field values obtained by the MP2 level of theory as a benchmark, it is shown that the B3LYP functional altered to include 40% Hartree–Fock exchange, which omits the bistable behaviour and calculates reasonably accurate critical electric fields.</p><h3>Graphical abstract</h3><p>Accurate electrostatic description of proton transfer reactions can be accomplished by incorporating 40% Hartree–Fock exchange to the standard B3LYP functional.</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142938760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co-sensitization of red and blue for dye-sensitized solar cells: A sequential approach","authors":"Maximilian Hupfer,&nbsp;Ruri Agung Wahyuono,&nbsp;Benjamin Dietzek-Ivanšić,&nbsp;Jonathan Plentz","doi":"10.1007/s12039-024-02330-1","DOIUrl":"10.1007/s12039-024-02330-1","url":null,"abstract":"<div><p>Combination of organic donor–linker–acceptor dyes for panchromatic enhancement in photoelectrodes of dye-sensitized solar cells enables their environmentally friendly and cost-effective design. A promising combination in terms of spectral broadening and miscibility are the dyenamo red and blue dyes, which differ only in their molecular structure via linkers. In this work, we investigate the sequential co-sensitization of both dyes together with the co-adsorption of aggregation inhibitor, chenodeoxycholic acid to increase the optical absorption and energy conversion efficiency. Finally, with a <i>J</i>_SC of 10.2 mA cm⁻² and a <i>V</i>_OC of 584 mV, a small increase was achieved.</p><h3>Graphical abstract</h3><p>Combining Dyenamo Red and Blue dyes with chenodeoxycholic acid in dye-sensitized solar cells enhances optical absorption and energy efficiency. These combination enable cost-effective, environmentally friendly designs by broadening the spectral range and improving miscibility through sequential co-sensitization and co-adsorption techniques.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142938746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Utilization of Fe3O4@MgO as a heterogeneous solid-base in functional group transformations of arylboronic acids, phenols and benzonitriles","authors":"Cho-Yeon Kim,&nbsp;Chae-Ri Lim,&nbsp;Seung-Hoi Kim","doi":"10.1007/s12039-024-02333-y","DOIUrl":"10.1007/s12039-024-02333-y","url":null,"abstract":"<div><p>Use of magnesium oxide-coated magnetite nanoparticles (Fe₃O₄@MgO) as a heterogeneous base-catalyst in organic functional group transformations has been demonstrated. Catalytic efficiency of the Fe₃O₄@MgO platform as an inorganic base-catalyst was firstly explored in the oxidative hydroxylation of arylboronic acids in the presence of aq. H₂O₂, affording the corresponding phenols with outstanding effectiveness. In addition, the direct <i>O</i>-benzylation of phenols catalyszed by the Fe₃O₄@MgO platform, was efficiently conducted in an aqueous environment, resulting in the formation of benzyl phenyl ethers. Lastly, the hydration of benzonitriles was also achieved when the Fe₃O₄@MgO platform was employed under aqueous conditions, yielding the corresponding benzamides.</p><h3>Graphic abstract</h3><p>Magnesium oxide-coated magnetite nanoparticles (Fe O @MgO) were used as a base catalyst in organic transformations. It efficiently catalyzed the oxidative hydroxylation of arylboronic acids, O-benzylation of phenols, and hydration of benzonitriles in aqueous conditions, producing phenols, benzyl phenyl ethers, and benzamides, respectively.</p>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142938762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Samarium cuprate with micron-size pores for drug sensing","authors":"Elena Korina,&nbsp;Arina Karaberova,&nbsp;Ekaterina Bulatova,&nbsp;Mikhail Golovin,&nbsp;Dalibor M. Stankovich,&nbsp;Sergei Gusev,&nbsp;Vladislav Fadeev,&nbsp;Oleg Bol’shakov","doi":"10.1007/s12039-024-02336-9","DOIUrl":"10.1007/s12039-024-02336-9","url":null,"abstract":"<div><p>Quick and robust analytical methods are of vital necessity in medicine and biology, making the synthesis of electroactive substrates for the sensing of medically relevant chemicals, a promising area of material science. Rare-earth cuprates, mostly famous for high-temperature superconductivity, continue to exhibit encouraging electroactivity towards surface selective oxidation of biologically active compounds. Samarium cuprate reported in this paper showed developed surface with unique porous morphology and good conductivity––a set of prerequisites for the sensing material. Further studies confirmed excellent samarium cuprate-based carbon paste-electrode sensitivity of enalapril maleate and helped to develop an analytical method with selectivity and stability applicable for wider use.</p><h3>Graphical abstract</h3><p>Sintering of equimolar amounts of copper and samarium oxides provides crystalline samarium cuprate at the temperature below its melting point. Obtained material has developed surface with micron-size pores. Further electrochemical studies as an additive in carbon paste, confirmed its excellent activity towards hypertension drug sensing.</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div><p> (<i>Note</i>: See more examples of graphical abstracts on the journal website, http://www.ias.ac.in/chemsci/index.html under ‘submission information’.)</p></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142938761","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"ab initio study of structure and energy of Be2+⋅(CO)1−3 complexes","authors":"Jamal N Dawoud,&nbsp;A K Sallabi","doi":"10.1007/s12039-024-02325-y","DOIUrl":"10.1007/s12039-024-02325-y","url":null,"abstract":"<div><p>Geometries and binding energies of Be²⁺ ⋅ (CO)_1–3 complexes have been determined at the level of MP2/aug-cc-pVTZ method. Binding energy increases linearly with the number of CO molecules in these complexes. Our results show that the sequential bond dissociation energy follows the order: <span>({text{Be}}^{2+}cdot text{CO})</span> <span>(&gt;)</span> <span>({text{Be}}^{2+}cdot {left(text{CO}right)}_{2})</span> <span>(&gt;{text{Be}}^{2+}cdot {left(text{CO}right)}_{3})</span>. This trend was well-explained in terms of ion–quadrupole interaction fluctuations. Detailed bond analysis confirmed that the strength of interaction between Be ion and CO molecule decreases with the number of CO molecules in these complexes. Our calculations show that the strength of interaction with these complexes is highly dependent on the CO bond polarization and stabilization energy of these complexes.</p><h3>Graphical abstract</h3><p>The sequential bond energies of the Be²⁺ ·(CO)^1,2,3 complexes follow the trend: Be²⁺ ·(CO) &gt; Be²⁺ ·(CO)₂ &gt; Be²⁺ ·(CO)₃ . The primary\u0000cause of the variations observed in the ion-quadruple attraction forces in these complexes is the strength of the σ-donation\u0000between the Be cation and CO molecules. The ion-induced dipole interaction energy in these complexes is insignificant.\u0000</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":616,"journal":{"name":"Journal of Chemical Sciences","volume":"137 1","pages":""},"PeriodicalIF":1.7,"publicationDate":"2025-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142925418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}