Retraction: L. Biesen, T.J.J. Müller, “Aggregation-Induced Emission-Active Donor-Substituted Aroyl-S,N-Ketene Acetals via Nucleophilic Amine Base Attack”, ChemPhotoChem2023, 7, e202300111, https://doi.org/10.1002/cptc.202300111.
The above article, published online on 25 August 2023 in Wiley Online Library (wileyonlinelibrary.com), has been retracted by agreement between the authors; the journal Editor-in-Chief, Deanne Nolan; Chemistry Europe; and Wiley-VCH GmbH.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.
撤回：L. Biesen, T.J.J. Müller, "Aggregation-Induced Emission-Active Donor-Substituted Aroyl-S,N-Ketene Acetals via Nucleophilic Amine Base Attack", ChemPhotoChem 2023, 7, e202300111, https://doi.org/10.1002/cptc.202300111.上述文章于 2023 年 8 月 25 日在线发表于 Wiley Online Library (wileyonlinelibrary.com)，经作者、期刊主编 Deanne Nolan、Chemistry Europe 和 Wiley-VCH GmbH 协议撤回。作者告知编辑，除了影响固态和集合量子产率测量的仪器误差外，化合物 3a、3c 和 3e 的结构分配也存在重大错误。因此，文章中报告的结论并不可靠。
{"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":"https://doi.org/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>\u0000<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The above article, published online on 25 August 2023 in Wiley Online Library (wileyonlinelibrary.com), has been retracted by agreement between the authors; the journal Editor-in-Chief, Deanne Nolan; Chemistry Europe; and Wiley-VCH GmbH.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":"21 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Valentine G. Nenajdenko, Victoria E. Shambalova, Alexander A. Aldoshin, Dmitry A. Bunin, Eugenia A. Safonova, Anna A. Moiseeva, Boris N. Tarasevich, Yulia G. Gorbunova
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‐1H‐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.
{"title":"Core‐Fluorinated BODIPYs ‐ a New Family of Highly Efficient Luminophores","authors":"Valentine G. Nenajdenko, Victoria E. Shambalova, Alexander A. Aldoshin, Dmitry A. Bunin, Eugenia A. Safonova, Anna A. Moiseeva, Boris N. Tarasevich, Yulia G. Gorbunova","doi":"10.1002/cptc.202400209","DOIUrl":"https://doi.org/10.1002/cptc.202400209","url":null,"abstract":"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‐1H‐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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"16 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-22","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}
Felix Glaser, Simon De Kreijger, Katerina Achilleos, Lakshmi Narayan Satheesh, Alexia Ripak, Noémie Chantry, Céline Bourgois, Sophie Quiquempoix, Joffrey Scriven, Julien Rubens, Milan Vander Wee-Léonard, Martin Daenen, Martin Gillard, Benjamin Elias, Ludovic Troian-Gautier
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 vs SCE for excited‐state oxidation and 0.14 to 1.48 V vs SCE for excited‐state reduction. A procedure for counter‐ion exchange to generate the corresponding PF6–, Cl–, BF4–, NO3–, OTf–, ClO4–, and BArF– 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.
本研究报告了含有取代的 2,2'-联吡啶、1,10-菲罗啉和重氮配体的共 32 种钌（II）和锇（II）光敏剂的一锅合成。虽然这些光敏剂中的大多数已在文献中报道过，但本研究提供了广泛的基态和激发态特性数据集，对机器学习、人工智能和光氧化催化等领域的未来发展非常有帮助。所有光敏剂都能强烈吸收光谱可见光部分的光，其中 Os(II) 光敏剂的吸收更进一步，达到红色部分。Ru(II) 光敏剂的激发态寿命和光致发光量子产率通常大于 Os(II) 类似物，这与能隙定律一致。对所有研究的光敏剂都测定了激发态氧化还原电位，激发态氧化电位为-0.21 至 -1.35 V vs SCE，激发态还原电位为 0.14 至 1.48 V vs SCE。报告了六种光敏剂生成相应的 PF6-、Cl-、BF4-、NO3-、OTf-、ClO4- 和 BArF- 的反离子交换过程。这些光敏剂易于合成，基本光物理性质报告详尽，激发态氧化还原电位范围广泛，为在多个应用领域进行系统研究提供了机会，并进一步促进了光氧化催化的发展。
{"title":"A Compendium of Methodically Determined Ground‐ and Excited‐State Properties of Homoleptic Ruthenium(II) and Osmium(II) Photosensitizers","authors":"Felix Glaser, Simon De Kreijger, Katerina Achilleos, Lakshmi Narayan Satheesh, Alexia Ripak, Noémie Chantry, Céline Bourgois, Sophie Quiquempoix, Joffrey Scriven, Julien Rubens, Milan Vander Wee-Léonard, Martin Daenen, Martin Gillard, Benjamin Elias, Ludovic Troian-Gautier","doi":"10.1002/cptc.202400134","DOIUrl":"https://doi.org/10.1002/cptc.202400134","url":null,"abstract":"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 vs SCE for excited‐state oxidation and 0.14 to 1.48 V vs SCE for excited‐state reduction. A procedure for counter‐ion exchange to generate the corresponding PF6–, Cl–, BF4–, NO3–, OTf–, ClO4–, and BArF– 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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"11 1","pages":""},"PeriodicalIF":3.7,"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}
In this report, a conductive polymer encapsulated metal oxide photocatalyst is developed through a straightforward insitu 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.
在本报告中，通过一种简单的原位合成方法，开发出了一种导电聚合物封装金属氧化物光催化剂，其中聚噻吩与二氧化钛纳米颗粒结合，增强了样品对可见光的吸收，并由于空位缺陷和高导电性显著提高了电荷转移效率，最终实现了优异的 H2 生成性能。值得注意的是，通过沉积简单的氧化还原介质，H2 的产生率得到了进一步提高。Co2+ 的引入促进了价带中光生成空穴的转移，使其从 +2 氧化态转变为 +3 氧化态，从而进一步实现了氧化机制。由于光生空穴的有效转移，激子的重组率大大降低，光催化产生 H2 的速率也得到提高。有趣的是，通过利用 Ti K-edge XANES 和 EXAFS 分析，确定了合成样品中 Ti 物种的价态和局部原子结构，验证了能量位置。
{"title":"Organic-Inorganic Hybrid Material for Photocatalytic H₂ Evolution: Electron Shuttling between Photoresponsive Nanocomposite and Co(II) Redox Mediator","authors":"Ashil Augustin, Manova Santhosh Yesupatham, Sulakshana Shenoy, M.D. Dhileepan, Bernaurdshaw Neppolian, KARTHIKEYAN SEKAR","doi":"10.1002/cptc.202400193","DOIUrl":"https://doi.org/10.1002/cptc.202400193","url":null,"abstract":"In this report, a conductive polymer encapsulated metal oxide photocatalyst is developed through a straightforward insitu 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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"5 1","pages":""},"PeriodicalIF":3.7,"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}
Philipp Groß, Sergey I. Druzhinin, Holger Schönherr, Heiko Ihmels
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 22AG (K = 1.0–44 ´ 105 M−2). Furthermore, fluorimetric analysis of thermal DNA denaturation (FRET melting) reveals a significant thermal stabilization of G4‐DNA 22AG 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 22AG. 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.
{"title":"Spectroscopic investigation of the quadruplex DNA‐binding properties of 9‐aryl‐substituted isoquinolinium derivatives","authors":"Philipp Groß, Sergey I. Druzhinin, Holger Schönherr, Heiko Ihmels","doi":"10.1002/cptc.202400241","DOIUrl":"https://doi.org/10.1002/cptc.202400241","url":null,"abstract":"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 22AG (K = 1.0–44 ´ 105 M−2). Furthermore, fluorimetric analysis of thermal DNA denaturation (FRET melting) reveals a significant thermal stabilization of G4‐DNA 22AG 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 22AG. 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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"44 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nina Hagmeyer, Alexander Schwab, Nabil Mroweh, Caitlin McManus, Maneesha Varghese, Jean-Marie Mouesca, Serge Gambarelli, Stephan Kupfer, Murielle Chavarot-Kerlidou, Benjamin Dietzek-Ivanšić
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 RuL1, 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 RuL1, where both redox equivalents are stored on the alloxazine‐based ligand.
{"title":"Spectroscopic Investigation of a Ruthenium Tris‐diimine Complex Featuring a Bioinspired Alloxazine Ligand","authors":"Nina Hagmeyer, Alexander Schwab, Nabil Mroweh, Caitlin McManus, Maneesha Varghese, Jean-Marie Mouesca, Serge Gambarelli, Stephan Kupfer, Murielle Chavarot-Kerlidou, Benjamin Dietzek-Ivanšić","doi":"10.1002/cptc.202400175","DOIUrl":"https://doi.org/10.1002/cptc.202400175","url":null,"abstract":"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 RuL1, 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 RuL1, where both redox equivalents are stored on the alloxazine‐based ligand.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"66 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Coumarinacyl Bromides as Unimolecular Photoinitiators for Conjugated Polymer Synthesis under Visible and NIR Light Irradiation","authors":"Mengdi Wan, Xiaoxuan Liu, Yusuf Yagci, Zhiquan Li","doi":"10.1002/cptc.202400196","DOIUrl":"https://doi.org/10.1002/cptc.202400196","url":null,"abstract":"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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"75 1 1","pages":""},"PeriodicalIF":3.7,"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}
Inés Sánchez-Movellán, Pablo García-Fernández, Juan María García-Lastra, José Antonio Aramburu, Miguel Moreno
This review is focused on 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, we deal with compounds involving d4 and d9 ions where the local structure of the involved MX6 complexes is distorted, a fact widely ascribed to the Jahn‐Teller (JT) effect. Nevertheless, that assumption is very 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 internal electric field due to the rest of lattice ions (ii) The existence of structural instabilities that lead to negative force constants. Then, we explore stable systems involving d3, d5 or d9 cations, where the internal electric field, ER, is responsible for some puzzling phenomena. This is the case of ruby and emerald. A similar situation holds when comparing the normal and the inverted perovskites. The role of ER is particularly remarkable looking for the origin of the color in the historical Egyptian Blue pigment
这篇综述的重点是过去二十年中提出的新观点，这些观点对于理解含有过渡金属（TM）阳离子的绝缘材料的光学特性起着关键作用。首先，我们将讨论涉及 d4 和 d9 离子的化合物，在这些化合物中，相关 MX6 复合物的局部结构是扭曲的，这一事实被广泛归因于 Jahn-Teller (JT) 效应。然而，这种假设往往是错误的，因为 JT 耦合要求在初始几何中存在轨道退化基态，而即使晶格为四方晶格，这一条件也无法满足。因此，d4 和 d9 复合物在低对称性晶格中的平衡几何受到两个因素的影响：(i) 由其余晶格离子产生的内部电场 (ii) 导致负力常数的结构不稳定性的存在。然后，我们探讨了涉及 d3、d5 或 d9 阳离子的稳定体系，在这些体系中，内部电场 ER 是一些令人费解的现象的原因。这就是红宝石和祖母绿的情况。在比较正常包晶和倒置包晶时，也会出现类似的情况。在寻找历史悠久的埃及蓝颜料的颜色起源时，ER 的作用尤为突出
{"title":"Internal electric fields and structural instabilities in insulating transition metal compounds: Influence on optical properties","authors":"Inés Sánchez-Movellán, Pablo García-Fernández, Juan María García-Lastra, José Antonio Aramburu, Miguel Moreno","doi":"10.1002/cptc.202400024","DOIUrl":"https://doi.org/10.1002/cptc.202400024","url":null,"abstract":"This review is focused on 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, we deal with compounds involving d4 and d9 ions where the local structure of the involved MX6 complexes is distorted, a fact widely ascribed to the Jahn‐Teller (JT) effect. Nevertheless, that assumption is very 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 internal electric field due to the rest of lattice ions (ii) The existence of structural instabilities that lead to negative force constants. Then, we explore stable systems involving d3, d5 or d9 cations, where the internal electric field, ER, is responsible for some puzzling phenomena. This is the case of ruby and emerald. A similar situation holds when comparing the normal and the inverted perovskites. The role of ER is particularly remarkable looking for the origin of the color in the historical Egyptian Blue pigment","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"122 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aika Yokoyama, Hanami Aoki, Mizuki Funayama, Ryo Shinozaki, Hiroto Yoshida, Dr. Akinobu Z. Suzuki, Prof. Dr. Toshiaki Furuta
The Front Cover 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 endoplasmic reticulum 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).
{"title":"Front Cover: Design, Synthesis, and Photochemical Properties of Gene-directed Caged RyR Probes for Photopharmacological Studies (ChemPhotoChem 8/2024)","authors":"Aika Yokoyama, Hanami Aoki, Mizuki Funayama, Ryo Shinozaki, Hiroto Yoshida, Dr. Akinobu Z. Suzuki, 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 Ca<sup>2+</sup> 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}
Long He, Jing Huang, Xingxing Zhang, Tianbing Ren, Lin Yuan
Rhodamine dyes have been extensively explored for bioimaging and therapeutic applications over the past few decades. However, it remains a challenge to design long‐wavelength and large Stokes shift rhodamine derivatives to meet the requirements of fluorescence imaging and phototherapy in deep living tissues. In this work, a pyridine aromatic unit was inserted into the ACF skeleton to prepare a series of stable rhodamine derivatives, ACFPs, to achieve long emission wavelength (> 650 nm) and large Stokes shift (~ 60 nm) by tuning the conjugated systems and electronic symmetry. More significantly, ACFPs are capable of continuously producing superoxide radical (O2‐•) under long wavelength irradiation. This study presents a novel paradigm for improving the optical properties of rhodamine, which has led to the development of a novel tool for image‐guided phototherapy for cancer treatment.
{"title":"Asymmetric π‐Extension Design of Long Wavelength Rhodamine Derivatives for Imaging and Phototherapy","authors":"Long He, Jing Huang, Xingxing Zhang, Tianbing Ren, Lin Yuan","doi":"10.1002/cptc.202400191","DOIUrl":"https://doi.org/10.1002/cptc.202400191","url":null,"abstract":"Rhodamine dyes have been extensively explored for bioimaging and therapeutic applications over the past few decades. However, it remains a challenge to design long‐wavelength and large Stokes shift rhodamine derivatives to meet the requirements of fluorescence imaging and phototherapy in deep living tissues. In this work, a pyridine aromatic unit was inserted into the ACF skeleton to prepare a series of stable rhodamine derivatives, ACFPs, to achieve long emission wavelength (> 650 nm) and large Stokes shift (~ 60 nm) by tuning the conjugated systems and electronic symmetry. More significantly, ACFPs are capable of continuously producing superoxide radical (O2‐•) under long wavelength irradiation. This study presents a novel paradigm for improving the optical properties of rhodamine, which has led to the development of a novel tool for image‐guided phototherapy for cancer treatment.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"16 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141882885","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}
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