ChemPhotoChem最新文献

{"title":"RETRACTION: Aggregation-Induced Emission-Active Donor-Substituted Aroyl-S,N-Ketene Acetals via Nucleophilic Amine Base Attack","authors":"","doi":"10.1002/cptc.202400248","DOIUrl":"10.1002/cptc.202400248","url":null,"abstract":"<p><b>Retraction</b>: L. Biesen, T.J.J. Müller, “Aggregation-Induced Emission-Active Donor-Substituted Aroyl-<i>S</i>,<i>N</i>-Ketene Acetals via Nucleophilic Amine Base Attack”, <i>ChemPhotoChem</i> <b>2023</b>, <i>7</i>, e202300111, https://doi.org/10.1002/cptc.202300111.</p><p>The above article, published online on 25 August 2023 in Wiley Online Library (wileyonlinelibrary.com), has been retracted by agreement between the authors; the journal Editor-in-Chief, Deanne Nolan; Chemistry Europe; and Wiley-VCH GmbH. The retraction has been agreed at the request of the authors, who informed the editor of significant errors in the structural assignment of compounds 3a, 3c and 3e, in addition to instrumental error affecting solid state and aggregate quantum yield measurements. As a result, the conclusions reported in the article are not considered reliable.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400248","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Core-Fluorinated BODIPYs – a New Family of Highly Efficient Luminophores","authors":"Victoria E. Shambalova,&nbsp;Alexander S. Aldoshin,&nbsp;Dmitry A. Bunin,&nbsp;Eugenia A. Safonova,&nbsp;Anna A. Moiseeva,&nbsp;Boris N. Tarasevich,&nbsp;Yulia G. Gorbunova,&nbsp;Valentine G. Nenajdenko","doi":"10.1002/cptc.202400209","DOIUrl":"10.1002/cptc.202400209","url":null,"abstract":"<p>A modular synthesis of novel series of 1,7-difluorinated BODIPYs has been elaborated. First, the acid-catalyzed condensation of ethyl 3-aryl-4-fluoro-1<i>H</i>-pyrrole-2-carboxylates with aromatic aldehydes gives the corresponding dipyrromethane-1,9-dicarboxylates. The latter are subjected to the exhaustive reduction with lithium aluminum hydride to transform the ester moieties into methyl groups. The subsequent oxidation of the resulting 1,9-dimethylated dipyrromethanes followed by the boron difluoride complexation afforded a family of novel core-fluorinated BODIPYs in up to 74 % yield. Photophysical properties of the resulting BODIPYs were tuned by varying of the starting fluoropyrroles and aromatic aldehydes and were studied by UV-visible and fluorescence spectroscopy. As a result, the fluorescence quantum yields of the obtained compounds reached up to 99 %. In addition, their ability to generate singlet oxygen and electrochemical properties were also evaluated. As a result, a new promising family of fluorophores with a good combination of the fluorescence and photosensitizing properties was obtained. It was found that conversion of ester groups into methyl ones at the 3,5-positions of the BODIPY core is a crucial step toward fluorescence enhancement. In addition, DFT calculations were performed to elucidate a relationship between electronic structure, geometry and photophysical properties of these BODIPYs.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217754","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":"A Compendium of Methodically Determined Ground- and Excited-State Properties of Homoleptic Ruthenium(II) and Osmium(II) Photosensitizers","authors":"Dr. Felix Glaser,&nbsp;Simon De Kreijger,&nbsp;Katerina Achilleos,&nbsp;Lakshmi Narayan Satheesh,&nbsp;Alexia Ripak,&nbsp;Noémie Chantry,&nbsp;Céline Bourgois,&nbsp;Sophie Quiquempoix,&nbsp;Joffrey Scriven,&nbsp;Julien Rubens,&nbsp;Dr. Milan Vander Wee-Léonard,&nbsp;Martin Daenen,&nbsp;Dr. Martin Gillard,&nbsp;Prof. Dr. Benjamin Elias,&nbsp;Prof. Dr. Ludovic Troian-Gautier","doi":"10.1002/cptc.202400134","DOIUrl":"10.1002/cptc.202400134","url":null,"abstract":"<p>The one-pot synthesis of a total of 32 ruthenium(II) and osmium(II) photosensitizers bearing substituted 2,2’-bipyridines, 1,10-phenanthrolines, and diaza ligands is reported. Whereas most of these photosensitizers were already reported in the literature, the present study offers extensive datasets of ground- and excited-state properties highly desirable for future development in e. g., machine learning, artificial intelligence, and photoredox catalysis. All photosensitizers absorbed light intensely in the visible part of the spectrum, with the Os(II) photosensitizers absorbing further into the red part. Excited-state lifetimes and photoluminescence quantum yields were generally larger for Ru(II) photosensitizers than for Os(II) analogs, which agrees with the energy gap law. The excited-state redox potentials were determined for all investigated photosensitizers covering a range of −0.21 to −1.35 V <i>vs</i>. SCE for excited-state oxidation and 0.14 to 1.48 V <i>vs</i>. SCE for excited-state reduction. A procedure for counterion exchange to generate the corresponding PF₆⁻, Cl⁻, BF₄⁻, NO₃⁻, OTf⁻, ClO₄⁻, and BAr^F− is reported for six photosensitizers. The synthetic ease, detailed report of fundamental photophysical properties, and a broad range of excited-state redox potentials open opportunities for systematic investigations in several applications and further streamline developments in photoredox catalysis.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217757","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":"Organic-Inorganic Hybrid Material for Photocatalytic H₂ Evolution: Electron Shuttling between Photoresponsive Nanocomposite and Co(II) Redox Mediator","authors":"Ashil Augustin,&nbsp;Manova Santhosh Yesupatham,&nbsp;Sulakshana Shenoy,&nbsp;M. D. Dhileepan,&nbsp;Bernaurdshaw Neppolian,&nbsp;Karthikeyan Sekar","doi":"10.1002/cptc.202400193","DOIUrl":"10.1002/cptc.202400193","url":null,"abstract":"<p>In this report, a conductive polymer encapsulated metal oxide photocatalyst is developed through a straightforward <i>insitu</i> synthesis method wherein, polythiophene is incorporated with TiO₂ nanoparticles which imparts enhanced visible-light absorption to the samples and significantly improves the efficiency of charge transfer resulting due to the vacancy defects and high conductivity, ultimately leading to exceptional performance in H₂ production. Significantly, the rate of H₂ production was enhanced even further through the deposition of simple redox mediator. The introduction of Co²⁺ facilitates the transfer of photogenerated holes from the valence band by its conversion from +2 to +3 oxidation state which further enables the oxidation mechanism. The recombination rate of excitons has been significantly reduced due to the efficient transfer of photogenerated holes and the rate of photocatalytic H₂ production is improved. Interestingly, the valence states and local atomic structure of the Ti species in the synthesized sample were ascertained through the utilization of Ti K-edge XANES and EXAFS analysis, which validated the energy position.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217758","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":"Spectroscopic Investigation of the Quadruplex DNA-Binding Properties of 9-Aryl-Substituted Isoquinolinium Derivatives","authors":"Philipp Groß,&nbsp;Dr. Sergey I. Druzhinin,&nbsp;Prof. Dr. Holger Schönherr,&nbsp;Prof. Dr. Heiko Ihmels","doi":"10.1002/cptc.202400241","DOIUrl":"10.1002/cptc.202400241","url":null,"abstract":"<p>The spectroscopic investigation of the binding properties of berberine-type 9-aryl-substituted isoquinolinium derivatives with G-quadruplex DNA (G4-DNA) are presented. Photometric titrations show that these ligands bind with high affinity to the telomeric G4-DNA form <b>22AG</b> (<i>K</i>=1.0–44×10⁵ M⁻²). Furthermore, fluorimetric analysis of thermal DNA denaturation (FRET melting) reveals a significant thermal stabilization of G4-DNA <b>22AG</b> upon association with the methoxy-substituted derivatives. As an analytically useful property, the derivatives with a phenyl substituent or with additional electron-donating groups show a very weak fluorescence intensity, which increased significantly upon G4-DNA complexation (fluorescence light-up effect). Additional time-resolved fluorescence spectroscopy indicated increased fluorescence lifetimes of the DNA-bound 9-(4-methoxyphenyl)-substituted derivative, when interacting with the quadruplex-forming strand <b>22AG</b>. Notably, the changes of the steady-state and time-resolved emission properties of the ligand are more pronounced with G4-DNA than with duplex DNA so that the combination of these complementary methods may be used for the selective G4-DNA detection.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400241","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217759","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spectroscopic Investigation of a Ruthenium Tris-Diimine Complex Featuring a Bioinspired Alloxazine Ligand","authors":"Nina Hagmeyer,&nbsp;Alexander Schwab,&nbsp;Dr. Nabil Mroweh,&nbsp;Dr. Caitilin McManus,&nbsp;Dr. Maneesha Varghese,&nbsp;Dr. Jean-Marie Mouesca,&nbsp;Dr. Serge Gambarelli,&nbsp;Dr. Stephan Kupfer,&nbsp;Dr. Murielle Chavarot-Kerlidou,&nbsp;Prof. Dr. Benjamin Dietzek-Ivanšić","doi":"10.1002/cptc.202400175","DOIUrl":"10.1002/cptc.202400175","url":null,"abstract":"<p>Molecular charge accumulating systems that act as both, photosensitizer and electron storage unit, are of interest in the context of multielectron redox processes, e. g. in solar fuel production. To this end, the photophysical properties of <b>RuL1</b>, a ruthenium tris-diimine complex with an alloxazine-based ligand as bioinspired structural motif, were investigated. The study includes absorption, emission, resonance Raman and transient absorption spectroscopy in combination with quantum chemical simulations to determine the light-driven reactivity of the complex. Moreover, spectroelectrochemistry was employed for an in-depth characterization of the optical properties of the reduced complex. Finally, a photolysis experiment using triethanolamine as electron source, in conjunction with redox titrations, demonstrated that visible light irradiation triggers the formation of the doubly-reduced singly-protonated derivative of <b>RuL1</b>, where both redox equivalents are stored on the alloxazine-based ligand.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400175","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217760","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Coumarinacyl Bromides as Unimolecular Photoinitiators for Conjugated Polymer Synthesis under Visible and NIR Light Irradiation","authors":"Mengdi Wan,&nbsp;Prof. Xiaoxuan Liu,&nbsp;Prof. Yusuf Yagci,&nbsp;Prof. Zhiquan Li","doi":"10.1002/cptc.202400196","DOIUrl":"10.1002/cptc.202400196","url":null,"abstract":"<p>Two coumarinacyl bromides, 3-(bromoacetyl)coumarin (BAC) and 3-(bromoacetyl)-7-methoxycoumarin (BACO), were developed for the photopolymerization of N-ethylcarbazole to construct conjugated polymer under visible and near-infrared light irradiation. BAC outperformed the conventional phenacyl bromide photoinitiator, exhibiting superior photoinitiation performance due to its optimal absorption characteristics and electron transfer efficiency. The obtained poly(N-ethylcarbazole) was thoroughly characterized, demonstrating the successful synthesis of a conjugated polymer with desired properties. Dedoping led to improved optical properties and film morphology. The polymerization mechanism was elucidated using transient absorption spectroscopy, revealing efficient electron transfer from the excited photoinitiators to N-ethylcarbazole.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217761","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":"Internal Electric Fields and Structural Instabilities in Insulating Transition Metal Compounds: Influence on Optical Properties","authors":"I. Sánchez-Movellán,&nbsp;P. García-Fernández,&nbsp;J. M. García-Lastra,&nbsp;J. A. Aramburu,&nbsp;M. Moreno","doi":"10.1002/cptc.202400024","DOIUrl":"10.1002/cptc.202400024","url":null,"abstract":"<p>This work reviews new ideas developed in the last two decades which play a key role for understanding the optical properties of insulating materials containing transition metal (TM) cations. Initially, this review deals with compounds involving d⁴ and d⁹ ions where the local structure of the involved MX₆ complexes (M=dⁿ cation, X=ligand) is never cubic but distorted, a fact widely ascribed to the Jahn-Teller (JT) effect. Nevertheless, that assumption is often wrong as the JT coupling requires an orbitally degenerate ground state in the initial geometry a condition not fulfilled even if the lattice is tetragonal. For this reason, the equilibrium geometry of d⁴ and d⁹ complexes in low symmetry lattices, is influenced by two factors: (i) The effects, usually ignored, of the internal electric field, <b>E</b>_R, due to the rest of lattice ions on the active electrons localized in the MX₆ unit. (ii) The existence of structural instabilities driven by vibronic interactions that lead to negative force constants. As first examples of these ideas, we show that the equilibrium structure, electronic ground state of KZnF₃:Cu²⁺, K₂ZnF₄:Cu²⁺ and K₂CuF₄ obey to different causes and only in KZnF₃:Cu²⁺ the JT effect takes place. These ideas also explain the local structure and optical properties of CuF₂, CrF₂ or KAlCuF₆ compounds where the JT effect is symmetry forbidden and those of layered copper chloroperovskites where the orthorhombic instability explains the red shift of one <i>d−d</i> transition under pressure. In a second step, this review explores stable systems involving d³, d⁵ or d⁹ cations, where the internal electric field, <b>E</b>_R, is responsible for some puzzling phenomena. This is the case of ruby and emerald that surprisingly exhibit a different color despite the Cr³⁺-O²⁻ distance is the same. A similar situation holds when comparing the normal (KMgF₃) and the inverted (LiBaF₃) perovskites doped with Mn²⁺ having the same Mn²⁺-F distance but clearly different optical spectra. The role of <b>E</b>_R is particularly remarkable looking for the origin of the color in the historical Egyptian Blue pigment based on CaCuSi₄O₁₀.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400024","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Front Cover: Design, Synthesis, and Photochemical Properties of Gene-directed Caged RyR Probes for Photopharmacological Studies (ChemPhotoChem 8/2024)","authors":"Aika Yokoyama,&nbsp;Hanami Aoki,&nbsp;Mizuki Funayama,&nbsp;Ryo Shinozaki,&nbsp;Hiroto Yoshida,&nbsp;Dr. Akinobu Z. Suzuki,&nbsp;Prof. Dr. Toshiaki Furuta","doi":"10.1002/cptc.202480801","DOIUrl":"https://doi.org/10.1002/cptc.202480801","url":null,"abstract":"<p><b>The Front Cover</b> illustrates the molecular structures of coumarin-caged ryanodine receptor (RyR) agonists and blockers. Photo-irradiation of a (6-bromo-7-hydroxycoumarin-4-yl)methyl (Bhc)-caged agonist released the active form, activated RyRs, and promoted Ca²⁺ release from the <i>endoplasmic reticulum</i> in mammalian cells. The photoreactivity of the caged RyR probes by 405 nm light was masked by the enzyme substrates, allowing cell-type-selective, enzyme gene-directed delivery of the caged RyR probes. More information can be found in the Research Article by A. Yokoyama, H. Aoki, T. Furuta et al. (DOI 10.1002/cptc.202400140).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 8","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202480801","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141980192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimization of the Structural Rigidity of a Deep-NIR Scaffold for Bioimaging","authors":"Xinru Hu,&nbsp;Yan Dong,&nbsp;Yuyang Zhang,&nbsp;Xiaohua Chen,&nbsp;Chuanbao Yuan,&nbsp;Danyang Wang,&nbsp;Prof. Xuhong Qian,&nbsp;Prof. Xiao Luo,&nbsp;Prof. Youjun Yang","doi":"10.1002/cptc.202400156","DOIUrl":"10.1002/cptc.202400156","url":null,"abstract":"<p>Bright deep-NIR dyes are actively sought after for their potential in fluorescence-guided surgery and disease theranostics. The major bottleneck lies with the rigidification of the conjugative backbone to suppress non-radiative deactivation. <b>EC5</b> is a notable deep-NIR absorbing/emitting scaffold, which we first reported in 2017. We recently discovered that its diphenyl ether moiety exhibited structural freedom, which was detrimental to its fluorescence brightness. We proposed to enhance the structural rigidity of <b>EC5</b> via ring-contraction, i. e., changing the diphenyl ether moiety of <b>EC5E</b> into a biphenyl of <b>EC5B</b>, its low-frequency normal modes were largely suppressed as predicted by theoretical calculations, and a 55.0 % increase of fluorescence brightness in CH₂Cl₂ was rendered experimentally. The bright <b>EC5B</b> was feasible for high-contrast <i>in vivo</i> imaging. <b>EC5B</b> has broad potential in practical biomedical applications.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141868705","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}