Journal of Photochemistry and Photobiology A-chemistry最新文献

{"title":"Coordination-driven molecular switch on the base of an ESIPT-capable pyrimidine ligand: Synthesis, fine-tuning of emission by the halide anion and theoretical studies","authors":"Nikita A. Shekhovtsov ,&nbsp;Elena B. Nikolaenkova ,&nbsp;Sofia Vorobyeva ,&nbsp;Alexey A. Ryadun ,&nbsp;Mark B. Bushuev","doi":"10.1016/j.jphotochem.2024.116091","DOIUrl":"10.1016/j.jphotochem.2024.116091","url":null,"abstract":"<div><div>ESIPT-based materials (ESIPT = Excited State Intramolecular Proton Transfer) find diverse applications in optoelectronics and biomedicine owing to the peculiarities of their luminescence properties. Here, an ESIPT-capable compound 2-(3,5-dimethyl-1<em>H</em>-pyrazol-1-yl)-4-(2-hydroxyphenyl)pyrimidine (<strong>HL^4,2,Me</strong>) featuring a short O–H⋅⋅⋅N intramolecular hydrogen bond and two N,N-sites for metal binding has been synthesized. <strong>HL^4,2,Me</strong> is the first reported molecule which can act as an ESIPT molecular switch triggered by metal ion coordination without its deprotonation. Drastic changes in the <strong>HL^4,2,Me</strong> conformation in the <strong>[Zn(HL^4,2,Me)X₂]</strong> (X = Cl, Br,<!--> <!-->I) complexes significantly alter the photoluminescence response compared to the free ligand. In the solid state, <strong>HL^4,2,Me</strong> exhibits barrierless ESIPT and large Stokes-shifted yellow-orange emission due to the interplay of anti-Kasha S₂ → S₀ fluorescence and Kasha-like T₁ → S₀ phosphorescence radiative channels. The violation of Kasha’s rule for <strong>HL^4,2,Me</strong> is justified by an extraordinarily large S₂ – S₁ energy gap (<em>ca.</em> 0.9 eV), slowing down the rate of S₂ → S₁ internal conversion. The photoluminescence behavior of the ESIPT–incapable zinc(II) coordination compounds strongly depends on the halide anion: the chlorido complex exhibits only fluorescence, the bromido complex displays a minor phosphorescence channel in addition to a major fluorescence channel, while the iodido complex exhibits predominantly phosphorescence. As a result, the emission color of the <strong>[Zn(HL^4,2,Me)X₂]</strong> complexes changes gradually from blue for X = Cl to orange for X = I, providing a platform for the fine-tuning of emission by the halide anion.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116091"},"PeriodicalIF":4.1,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539799","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":"Sensitive photoelectrochemical aptasensing of Salmonella enteritidis based on AgBiS2 and Ag/g-C3N4 with gold nanoparticles","authors":"Yifan Wang ,&nbsp;Haoran Cheng ,&nbsp;Ze Cheng ,&nbsp;Gongliang Zhang ,&nbsp;Hongman Hou ,&nbsp;Jingran Bi ,&nbsp;Shuang Yan ,&nbsp;Hongshun Hao","doi":"10.1016/j.jphotochem.2024.116093","DOIUrl":"10.1016/j.jphotochem.2024.116093","url":null,"abstract":"<div><div>In this paper, an ultrasensitive photoelectric chemical sensor based on AgBiS₂ and Ag/g-C₃N₄ was prepared for the detection of <em>Salmonella enteritidis</em> (SE). The AgBiS₂ and Ag/g-C₃N₄ were modified on FTO by layer modification to increase the photoelectric activity of the electrode, the gold nanoparticles continued to be modified, and the aptamer of SE was fixed by Au<img>S bond to realize the specific detection of SE. Compared with the AgBiS₂-modified electrode, the electrode prepared by the composite material produced a significantly enhanced and stable photocurrent signal under Xe lamp irradiation. The detection limit of sensor was 2.18 CFU/mL, and ideally, the concentration of SE detection would show a good linear relationship between 6.72 × 10³ CFU/mL and 6.72 × 10⁸ CFU/mL. The constructed photoelectrochemical sensor has strong sensitivity, wide linear range, and good selectivity for potential pathogenic bacteria. Therefore, this study provides a very promising photoelectric chemical platform for the detection of SE.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116093"},"PeriodicalIF":4.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539796","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":"Preparation of g-C3N4 from mixed ammonium salts containing NH4SCN and characterization of its cobalt-modified photocatalytic degradation of formaldehyde","authors":"Xuejun Wang,&nbsp;Mai Wei,&nbsp;Liwei Ma,&nbsp;Shaonan Shan,&nbsp;Guoqiang Li,&nbsp;Xiaozhong Wang,&nbsp;Guojie Zhang","doi":"10.1016/j.jphotochem.2024.116097","DOIUrl":"10.1016/j.jphotochem.2024.116097","url":null,"abstract":"<div><div>This paper aims to achieve high-quality utilization of desulfurization waste liquid mixed salt. CN-MIX was prepared through pyrolysis of a mixture containing ammonium thiocyanate, ammonium thiosulfate, and ammonium sulfate. Additionally, CN-MIX/Co-a was produced via an impregnation-pyrolysis method with cobalt modification. The performance of the photocatalysts was evaluated using the formaldehyde degradation rate as an index, and their stability was tested. The results indicate that the specific surface area and pore volume of CN-MIX/Co-a increase by 1.53-fold and 1.44-fold, respectively, compared to CN prepared from single salt. The cobalt loading inhibits the thermal polymerization of CN-MIX, leading to a reduction in the intensity of the (0<!--> <!-->0<!--> <!-->2) crystal diffraction peaks. Additionally, CN-MIX/Co-a exhibits an increase in the C<img>N peak at 2000–2200 cm⁻¹, generating more photocatalytic active sites. The absorption sideband in the visible range red-shifts from 429 nm to 458 nm, broadening the photoresponse range. The emission peak in the photoluminescence (PL) diagram decreases, reducing the photogenerated electron-hole recombination rate. The photocatalyst demonstrates enhanced photocatalytic degradation of formaldehyde gas, with the degradation rate of CN-MIX/Co-a increasing from 13.28 % to 99.2 %. Furthermore, after eight cycles of use, the degradation efficiency of CN-MIX/Co-a for formaldehyde remains above 90 %, indicating high stability.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116097"},"PeriodicalIF":4.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539797","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 of magnetic polystyrene nanocomposite by emulsion polymerization using a photo-responsive emulsifier for efficient crude oil absorption","authors":"Hadi Rostamipoor ,&nbsp;Hanie Ahmadi ,&nbsp;Vahid Haddadi-Asl ,&nbsp;Majid Moussaei ,&nbsp;Hossein Roghani-Mamaqani","doi":"10.1016/j.jphotochem.2024.116092","DOIUrl":"10.1016/j.jphotochem.2024.116092","url":null,"abstract":"<div><div>Both human health and marine life are seriously threatened by crude oil spills into bodies of water. For effective crude oil spill cleaning, we created a magnetic polystyrene (m-PS) nanocomposite. The use of magnetic nanoparticles makes crude oil absorption more environmentally friendly by making it easier to collect and recycle using an external magnetic field. To make Fe₃O₄ nanoparticles compatible with the hydrophobic styrene monomer used in emulsion polymerization, they were treated using a hydrophobic surface modification reaction. This alteration facilitated the grafting of polystyrene (PS) chains onto the nanoparticles, which then underwent emulsion polymerization. As an emulsifier, a light-responsive amphiphilic block copolymer containing coumarin was created via reversible addition-fragmentation chain transfer polymerization. This allowed for regulated emulsification and demulsification in response to UV stimulation. The synthesized m-PS nanocomposite demonstrated a crude oil absorption capacity of up to 2.31 times of its own weight, indicating its high efficiency for crude oil spill cleanup. The synthetic emulsifier exhibited a significantly lower critical micelle concentration compared to the commercial P105 emulsifier (0.0976 against 0.354 mg/mL, respectively), indicating higher efficiency and reduced environmental impact. For a more thorough comprehension of the reported results, we also assessed the Hofmeister effect in PS produced using commercial and synthetic emulsifiers.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116092"},"PeriodicalIF":4.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539837","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":"Remarkable NH3 gas sensing performance of spray deposited Tb doped WO3 thin films at room temperature","authors":"Devarajan Alagarasan ,&nbsp;S.S. Hegde ,&nbsp;R. Naik ,&nbsp;Hitha D. Shetty ,&nbsp;H.B. Shiva Prasad ,&nbsp;Thamraa Alshahrani ,&nbsp;S. AlFaify ,&nbsp;Mohd. Shkir","doi":"10.1016/j.jphotochem.2024.116087","DOIUrl":"10.1016/j.jphotochem.2024.116087","url":null,"abstract":"<div><div>To evade potential health hazards associated with exposure to NH₃, there has been an increasing demand for efficient gas sensors operating at room temperature (RT). In this study, thin films of Tb-doped (0–5 wt%) WO₃ synthesized by spray pyrolysis technique are used as a novel material for sensing NH₃ gas. The X-ray diffraction (XRD) pattern identified the hexagonal crystal system of WO₃ films and increased crystallinity for the 2 wt% Tb-doing concentration. Field emission scanning electron microscopy (FE-SEM) unveiled the distinct surface morphology of mesh-like porous structures for Tb-doped films suitable for the target gas adsorption/desorption process. Multiple photoluminescence (PL) emission peaks indicate the presence of defect states, including defect energy levels created by oxygen vacancies (O_v). Optical analysis indicated shrinkage of the bandgap of WO₃ thin films for doping levels up to 2 wt%. Among all gas sensors, 2 wt% Tb-doped WO₃ exhibited exceptionally high response and low response time at 250 ppm NH₃ concentrations measured at room temperature (RT). The sensor’s performance for NH₃ gas sensing is compared with previous reports on WO₃-based NH₃ sensors. The gas sensing mechanism in WO₃ is also briefly discussed.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116087"},"PeriodicalIF":4.1,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539795","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":"Eco-friendly synthesis and applications of graphene-titanium dioxide nanocomposites for pollutant degradation and energy storage","authors":"Nazish Parveen ,&nbsp;Sajid Ali Ansari ,&nbsp;Kholoud M. Alnahdi ,&nbsp;Hassan H. Hammud ,&nbsp;Waleed A. Aljamhi ,&nbsp;Mir Waqas Alam ,&nbsp;Syed Farooq Adil ,&nbsp;Wail Al Zoubi","doi":"10.1016/j.jphotochem.2024.116096","DOIUrl":"10.1016/j.jphotochem.2024.116096","url":null,"abstract":"<div><div>An innovative, eco-friendly method has been developed to synthesize reduced graphene oxide (rGO) sheets using orange peel extract. Following this, TiO₂ nanoparticles are anchored to the rGO sheets through a hydrothermal process, resulting in an rGO/TiO₂ nanocomposite (GTO/NC). This study utilized standard characterization techniques to confirm the formation of GTO/NC-1 and GTO/NC-2. Comparative analysis demonstrated that orange peel extract exhibits reducing capabilities compared to other natural reducers. The resulting GTO/NC-1 and GTO/NC-2, specifically GTO/NC-2, enhanced catalytic performance in degrading methyl orange a prevalent organic pollutant in various industrial applications. This nanocomposite achieved a turnover frequency of 0.003 mg MO/mg catalyst/min and displayed remarkable durability, enduring 3.0 cycles with robust first-order rate constants of 0.0193 min⁻¹. Additionally, the electrochemical properties of GTO/NC-1 and GTO/NC-2 as electrode materials were assessed, revealing a specific capacitance of 320.0 Fg⁻¹ at a current density of 1.0 Ag⁻¹ and maintaining about 86.8 % of its initial capacitance after various charge–discharge cycles. These properties highlight the potential of GTO/NC-1 and GTO/NC-2 as both efficient catalysts for environmental remediation and durable materials for energy storage applications, offering substantial benefits for sustainable technology solutions.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116096"},"PeriodicalIF":4.1,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539798","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":"Thienothiophene based AIE-Active bulky materials for sensitive explosive detection","authors":"Recep Isci ,&nbsp;Bleda Can Sadikogullari ,&nbsp;Berkay Sütay ,&nbsp;Bunyamin Karagoz ,&nbsp;Ayse Daut Ozdemir ,&nbsp;Turan Ozturk","doi":"10.1016/j.jphotochem.2024.116095","DOIUrl":"10.1016/j.jphotochem.2024.116095","url":null,"abstract":"<div><div>Sensors for selective and sensitive detection of nitroaromatic (NAC) explosives are of current interest for both national security and environmental protection. In this work, three thienothiophene based AIE active materials (TPE2-TT, TPE3-TT and TPE3-TPA-TT), possessing tetraphenylethylene and triphenylamine units, were designed and synthesized as chemosensors for sensitively detecting 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT) and trinitrophenol (TNP) explosives. Among the AIEgens, TPE3-TT demonstrated a maximum Stern-Volmer constant (K_sv) reaching to 2.9 x 10⁴ M⁻¹ by quenching response toward TNP. They exhibited vivid visual quenching on absorbent papers. Moreover, probe-explosive complex interactions and their mechanisms were investigated using density functional theory (DFT). Their remarkable properties indicated that TT based AIEgens are promising probes for sensitively detecting the explosives, which provided a new source of potential leading to new designs for detection of explosives.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116095"},"PeriodicalIF":4.1,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539842","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":"Growth of dendritic CuS nanostructures for photoacoustic image guided Chemo-Photothermal therapy","authors":"A. Gangwar ,&nbsp;Sonali Gupta ,&nbsp;Jagriti Gupta ,&nbsp;Bijaideep Dutta ,&nbsp;Neha Dubey ,&nbsp;Sandeep B. Shelar ,&nbsp;N. Singh ,&nbsp;S.K. Biswas ,&nbsp;P.A. Hassan ,&nbsp;K.C. Barick","doi":"10.1016/j.jphotochem.2024.116084","DOIUrl":"10.1016/j.jphotochem.2024.116084","url":null,"abstract":"<div><div>Herein, we report a unique method for design and development of carboxyl enriched dendritic CuS nanostructures (CuS NSs) for photoacoustic image guided chemo-photothermal therapy. The dendritic network was grown on the surface of CuS nanoparticles via layer-by-layer assembly of amino acid. XRD and TEM studies established the formation of crystalline well-spherical nanosized hexagonal covellite (CuS) phase. The successful growth of dendritic structure was apparent from the rise in surface charge, hydrodynamic diameter and characteristic vibrational band intensity of peptide bonds. The developed different generations of dendritic CuS NSs (D⁰-CuS NSs, D¹-CuS NSs, D²-CuS NSs and D³-CuS NSs) displayed wide-ranging absorption band in near infrared (NIR) zone and exhibited good photothermal heating efficacy upon irradiation of 980 nm laser light. From <em>in</em>-<em>vitro</em> cellular studies, it has been found that the NIR irradiation effectively enhanced the photothermal toxicity of D³-CuS NSs towards cancer cells. Moreover, these negatively charged water-dispersible D³-CuS NSs were conjugated with positively charged anticancer drug, doxorubicin hydrochloride (DOX) through electrostatic interaction. The DOX loaded D³-CuS NSs (DOX@D³-CuS NSs) revealed pH dependent drug release behaviour and their considerable uptake in breast cancer cells (MCF-7). Further, DOX@D³-CuS NSs exhibited a much higher toxicity towards cancer cells upon NIR light over individual counterparts suggesting their strong ability for chemo-photothermal therapy. Moreover, these biocompatible CuS NSs have shown excellent concentration dependent photoacoustic properties at pulse laser excitation (850 nm) and thus, they can be found potential application in chemo-photothermal therapy.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116084"},"PeriodicalIF":4.1,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539793","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, Characterization of KNb0.99Eu0.01O3 and improved Photo-catalytic H2-Production on Ag/La2NiO4/ KNb0.99Eu0.01O3 hetero-junction","authors":"R. Mekersi ,&nbsp;S. Boumaza ,&nbsp;A. Bahdaouia ,&nbsp;S. Benallal ,&nbsp;A. Boudjemaa ,&nbsp;M. Trari","doi":"10.1016/j.jphotochem.2024.116094","DOIUrl":"10.1016/j.jphotochem.2024.116094","url":null,"abstract":"<div><div>The perovskite KNb_0.99Eu_0.01O₃ prepared by nitrate combustion is applied as a hydrogen photocathode in heterojunction with La₂NiO₄ under visible light. The XRD pattern confirms the formation of KNb_0.99Eu_0.01O₃ structure with orthorhombic single phase. The SEM images present grains between 0.2 and 0.4 µm while the optical band gap (3.14 eV) is calculated from the diffuse reflectance. Under illumination, the cyclic voltammetry (CV) and the capacitance measurements in Na₂SO₄ electrolyte show an increased current below ∼ -0.7 V vs. Ag/AgCl and <em>p</em>-type behavior with a conduction band (CB = −1.95 V) cathodically positioned with respect to H₂ level, thus leading to H₂ photo-production. The hetero-system La₂NiO₄/KNb_0.99Eu_0.01O₃ shows a much higher activity than KNb_0.99Eu_0.01O₃ where efficient H₂-photoevolution occurs with concomitant oxidation of S₂O₃²⁻, as reducing agent. So, the co-junction of La₂NiO₄ with KNb_0.99Eu_0.01O₃ facilitates the charge transfer and increases the reaction efficiency. At neutral pH, the H₂ evolution rate for the photocatalysts KNb_0.99Eu_0.01O₃ and La₂NiO₄/ KNb_0.99Eu_0.01O₃ are 11.15 and 57 µmol g⁻¹ min⁻¹; respectively. Further enhancement is observed with Ag-loaded La₂NiO₄/KNb_0.99Eu_0.01O₃, reaching a maximum hydrogen production rate of 67 µmol g⁻¹ min⁻¹, attributed to the lower overpotential introduced by Ag. These findings highlight the potential of the ternary system Ag/La₂NiO /KNb_0.99Eu_0.01O₃ as an efficient photocathode for H₂ generation.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116094"},"PeriodicalIF":4.1,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539844","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":"Induced of axial chirality in near-infrared-absorbing ball-shaped ruthenium complexes","authors":"Yoshitaka Shinokubo ,&nbsp;Ryo Arai ,&nbsp;Tatsuya Nishimura ,&nbsp;Katsuhiro Maeda ,&nbsp;Hajime Maeda ,&nbsp;Masahito Segi ,&nbsp;Taniyuki Furuyama","doi":"10.1016/j.jphotochem.2024.116089","DOIUrl":"10.1016/j.jphotochem.2024.116089","url":null,"abstract":"<div><div>Ball-shaped metal complexes that absorb in the near-infrared (NIR) region can be synthesized in a single step. Although stereogenic-at-metal complexes have been obtained, the induction of axial chirality has not yet been demonstrated. In this study, NIR-absorbing ball-shaped ruthenium complexes with axial chirality were facilely synthesized using asymmetric diiminoisoindoline derivatives. Despite lacking a discrete point chiral moiety, these complexes exhibited molecular chirality. The incorporation of bulky substituents facilitated enantiomeric differentiation. High-performance liquid chromatography (HPLC) with a chiral column enabled the isolation of the pure enantiomers as stable compounds. The absolute configurations of these isomers were revealed using vibrational circular dichroism (VCD) spectroscopy. The characteristic peaks originating from ligand vibrations exhibited distinct mirror images, and the experimental spectra were well reproduced by theoretical calculations. This methodology has broad applicability for the development of chiral ball-shaped metal complexes as NIR materials.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"459 ","pages":"Article 116089"},"PeriodicalIF":4.1,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142539794","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}