Carbon dioxide (CO2) is the primary greenhouse gas responsible for global warming, posing a significant challenge to the global environment. To reduce CO2 emission and support the sustainable development, efficient conversion of CO2 into chemical feedstocks has gained a lot of attention. One promising strategy inspired by natural photosynthesis is solar-driven CO2 reduction, which uses appropriate photocatalytic systems to generate CO, HCOOH, CH4, CH3OH, etc. However, developing low-cost, environmentally friendly, and non-toxic materials for the catalytic conversion of CO2 remains a significant challenge. Light-absorbing photosensitizers play an important role in photocatalytic systems. Recently, non-precious metal photosensitizers such as organic compounds and earth-abundant metal complexes have been intensively studied for developing low-cost photocatalytic systems. This review focuses on recent reports on organic and non-precious metal photosensitizers for photocatalytic CO2 reduction.
{"title":"Organic and Non-Precious Metal Photosensitizers for Photocatalytic CO2 Reduction","authors":"Yilin Xue, Duobin Chao","doi":"10.1002/cptc.202400246","DOIUrl":"10.1002/cptc.202400246","url":null,"abstract":"<p>Carbon dioxide (CO<sub>2</sub>) is the primary greenhouse gas responsible for global warming, posing a significant challenge to the global environment. To reduce CO<sub>2</sub> emission and support the sustainable development, efficient conversion of CO<sub>2</sub> into chemical feedstocks has gained a lot of attention. One promising strategy inspired by natural photosynthesis is solar-driven CO<sub>2</sub> reduction, which uses appropriate photocatalytic systems to generate CO, HCOOH, CH<sub>4</sub>, CH<sub>3</sub>OH, etc. However, developing low-cost, environmentally friendly, and non-toxic materials for the catalytic conversion of CO<sub>2</sub> remains a significant challenge. Light-absorbing photosensitizers play an important role in photocatalytic systems. Recently, non-precious metal photosensitizers such as organic compounds and earth-abundant metal complexes have been intensively studied for developing low-cost photocatalytic systems. This review focuses on recent reports on organic and non-precious metal photosensitizers for photocatalytic CO<sub>2</sub> reduction.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217742","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}
The fluorescent probe provides a simple for detecting Cu2+ through fluorescence quenching of the Schiff-base probes by Cu2+. However, the azine-based probes often suffer from poor solubility and dispersibility in water and are easily interfered with by other competing ions, which significantly reduces their applicable potential. In this study, we synthesized a water-dissoluble and highly fluorescent γ-Cyclodextrin (γ-CD)/2-hydroxybenzaldehyde azine (2-HBA) inclusion complex for Cu2+ detection. The inclusion of 2-HBA into γ-CD enhances its solubility in water and allows it to emit fluorescence. The as-synthesized γ-CD/2-HBA probe exhibits high sensitivity for colorimetric and fluorescent detection of Cu2+, with detection limits reaching 2.72 and 1.53 nM, respectively. The results exceed most of those reported in the literature. The probe's structure and potential mechanism were systematically analysed using the experimental and theoretical methods.
{"title":"2-Hydroxybenzaldehyde Azine and γ-Cyclodextrin Based Colorimetric/Fluorescent Probe for Highly Sensitive and Selective Detection of Cu2+","authors":"Vigneshkumar Ganesan, Chandramohan Govindasamy, Esakkimuthu Shanmugasundaram, Kannan Vellaisamy, Nithesh Kumar Krishnan, Murali Krishnan Mani, Selvam Kaliyamoorthy, Bo-Tau Liu, Stalin Thambusamy","doi":"10.1002/cptc.202400170","DOIUrl":"10.1002/cptc.202400170","url":null,"abstract":"<p>The fluorescent probe provides a simple for detecting Cu<sup>2+</sup> through fluorescence quenching of the Schiff-base probes by Cu<sup>2+</sup>. However, the azine-based probes often suffer from poor solubility and dispersibility in water and are easily interfered with by other competing ions, which significantly reduces their applicable potential. In this study, we synthesized a water-dissoluble and highly fluorescent γ-Cyclodextrin (γ-CD)/2-hydroxybenzaldehyde azine (2-HBA) inclusion complex for Cu<sup>2+</sup> detection. The inclusion of 2-HBA into γ-CD enhances its solubility in water and allows it to emit fluorescence. The as-synthesized γ-CD/2-HBA probe exhibits high sensitivity for colorimetric and fluorescent detection of Cu<sup>2+</sup>, with detection limits reaching 2.72 and 1.53 nM, respectively. The results exceed most of those reported in the literature. The probe's structure and potential mechanism were systematically analysed using the experimental and theoretical methods.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217743","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}
Baldeep K. Sidhu, Issiah B. Lozada, Rathiesh Pandian, Ibrahim Alfurayj, Clemens Burda, David E. Herbert
Pyrimidines, a prominent isomer class of diazines, are promising molecular constituents of electron-deficient luminescent and hole-transport materials. Here, we report the fluorescence lifetimes and describe the electronic structures and character of low-lying emissive excited states of a series of synthetically accessible donor-acceptor-donor (D−A−D′) and donor-acceptor-acceptor (D−A−A′) type pyrimidines, including both all-organic and hybrid organic-organometallic analogues. We find that strategically varying the aryl substituents on a pyrimidine enables tuning of the character of the luminescent excited states from charge-transfer (CT) to locally excited (LE) states, which then differ in their sensitivity to their environment. This study suggests structural handles for controlling the photophysics of arylpyrimidines relevant to a variety of applications for luminescent materials.
{"title":"Experimental and Computational Investigation of the Photophysical Properties of a Series of Luminescent D−A−D’ and D−A−A’ Pyrimidines","authors":"Baldeep K. Sidhu, Issiah B. Lozada, Rathiesh Pandian, Ibrahim Alfurayj, Clemens Burda, David E. Herbert","doi":"10.1002/cptc.202400216","DOIUrl":"10.1002/cptc.202400216","url":null,"abstract":"<p>Pyrimidines, a prominent isomer class of diazines, are promising molecular constituents of electron-deficient luminescent and hole-transport materials. Here, we report the fluorescence lifetimes and describe the electronic structures and character of low-lying emissive excited states of a series of synthetically accessible donor-acceptor-donor (D−A−D′) and donor-acceptor-acceptor (D−A−A′) type pyrimidines, including both all-organic and hybrid organic-organometallic analogues. We find that strategically varying the aryl substituents on a pyrimidine enables tuning of the character of the luminescent excited states from charge-transfer (CT) to locally excited (LE) states, which then differ in their sensitivity to their environment. This study suggests structural handles for controlling the photophysics of arylpyrimidines relevant to a variety of applications for luminescent materials.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 12","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202400216","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217755","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}
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":"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}
Victoria E. Shambalova, Alexander S. Aldoshin, Dmitry A. Bunin, Eugenia A. Safonova, Anna A. Moiseeva, Boris N. Tarasevich, Yulia G. Gorbunova, Valentine G. Nenajdenko
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":"Victoria E. Shambalova, Alexander S. Aldoshin, Dmitry A. Bunin, Eugenia A. Safonova, Anna A. Moiseeva, Boris N. Tarasevich, Yulia G. Gorbunova, 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}
Dr. Felix Glaser, Simon De Kreijger, Katerina Achilleos, Lakshmi Narayan Satheesh, Alexia Ripak, Noémie Chantry, Céline Bourgois, Sophie Quiquempoix, Joffrey Scriven, Julien Rubens, Dr. Milan Vander Wee-Léonard, Martin Daenen, Dr. Martin Gillard, Prof. Dr. Benjamin Elias, Prof. Dr. 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 counterion 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":"Dr. Felix Glaser, Simon De Kreijger, Katerina Achilleos, Lakshmi Narayan Satheesh, Alexia Ripak, Noémie Chantry, Céline Bourgois, Sophie Quiquempoix, Joffrey Scriven, Julien Rubens, Dr. Milan Vander Wee-Léonard, Martin Daenen, Dr. Martin Gillard, Prof. Dr. Benjamin Elias, 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 PF<sub>6</sub><sup>−</sup>, Cl<sup>−</sup>, BF<sub>4</sub><sup>−</sup>, NO<sub>3</sub><sup>−</sup>, OTf<sup>−</sup>, ClO<sub>4</sub><sup>−</sup>, and BAr<sup>F−</sup> 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}
Ashil Augustin, Manova Santhosh Yesupatham, Sulakshana Shenoy, M. D. Dhileepan, Bernaurdshaw Neppolian, Karthikeyan Sekar
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":"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 TiO<sub>2</sub> 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 H<sub>2</sub> production. Significantly, the rate of H<sub>2</sub> production was enhanced even further through the deposition of simple redox mediator. The introduction of Co<sup>2+</sup> 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 H<sub>2</sub> 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}
Philipp Groß, Dr. Sergey I. Druzhinin, Prof. Dr. Holger Schönherr, Prof. Dr. 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, Dr. Sergey I. Druzhinin, Prof. Dr. Holger Schönherr, 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>=1.0–44×10<sup>5</sup> M<sup>−2</sup>). 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}
Nina Hagmeyer, Alexander Schwab, Dr. Nabil Mroweh, Dr. Caitilin McManus, Dr. Maneesha Varghese, Dr. Jean-Marie Mouesca, Dr. Serge Gambarelli, Dr. Stephan Kupfer, Dr. Murielle Chavarot-Kerlidou, Prof. Dr. 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, Dr. Nabil Mroweh, Dr. Caitilin McManus, Dr. Maneesha Varghese, Dr. Jean-Marie Mouesca, Dr. Serge Gambarelli, Dr. Stephan Kupfer, Dr. Murielle Chavarot-Kerlidou, 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}
Mengdi Wan, Prof. Xiaoxuan Liu, Prof. Yusuf Yagci, Prof. Zhiquan Li
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, Prof. Xiaoxuan Liu, Prof. Yusuf Yagci, 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}