ChemPhotoChemPub Date : 2024-09-12DOI: 10.1002/cptc.202400235
Tim Silies, Nikos L. Doltsinis, Constantin G. Daniliuc, Fabio Rizzo
{"title":"Fluorene vs. Spirobifluorene: Effect of the π‐System on TADF Properties","authors":"Tim Silies, Nikos L. Doltsinis, Constantin G. Daniliuc, Fabio Rizzo","doi":"10.1002/cptc.202400235","DOIUrl":"https://doi.org/10.1002/cptc.202400235","url":null,"abstract":"There are many options to design a molecular structure that could result in thermally activated delayed fluorescence (TADF). One promising strategy is to use the donor‐π‐acceptor motive where an electron‐donating unit is linked to an electron‐acceptor via an aryl moiety like phenyl. While this approach is widely used and well understood, the performance of the chromophores can be limited by different energy loss pathways, e.g. internal conversion or by π‐stacking. To circumvent these problems rigid structures with sterically demanding substituents are applied. In this work, we designed two TADF emitters based on phenothiazine and nitrile linked via spiro‐9,9’‐bi[fluorene] or 9,9‐dimethylfluorene and compared the effect of the linker on the physical properties of the dyes. This work emphasizes the importance of careful design of conjugated spacer for efficient TADF emitters.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"14 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217781","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":"Enhancement of Circularly Polarized Luminescence Brightness of Schiff‐base Diphenylboron and 9‐Borafluoren‐9‐yl Complexes","authors":"Masahiro Ikeshita, Shinya Watanabe, Taichi Oka, Ayumu Kuroda, Seika Suzuki, Daiya Suzuki, Yoshitane Imai, Takashi Tsuno","doi":"10.1002/cptc.202400265","DOIUrl":"https://doi.org/10.1002/cptc.202400265","url":null,"abstract":"A series of diphenylboron and 9‐borafluoren‐9‐yl complexes with chiral Schiff‐base ligands was synthesized and characterized by NMR spectroscopy. X‐ray diffraction analysis revealed that their boron centers were adapted to tetrahedral coordination geometry. Although boron complexes with salicylideneimine backbones exhibited a weak circularly polarized luminescence (CPL), the CPL brightness (BCPL) was enhanced more than 9‐fold by the π‐extension of the Schiff base ligands. Time‐resolved emission decay analysis and theoretical calculations based on density functional theory (DFT) were conducted to further understand their luminescent properties.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"13 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217783","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}
ChemPhotoChemPub Date : 2024-09-10DOI: 10.1002/cptc.202480901
Grazia M. L. Consoli, Giuseppe Forte, Ludovica Maugeri, Salvatore Petralia
{"title":"Front Cover: Photo-Responsive TiO2-Gold Nanoparticle-Polymer Nanohybrid Exhibits Photothermal, Thermo-Release, and Photocatalytic Effects (ChemPhotoChem 9/2024)","authors":"Grazia M. L. Consoli, Giuseppe Forte, Ludovica Maugeri, Salvatore Petralia","doi":"10.1002/cptc.202480901","DOIUrl":"https://doi.org/10.1002/cptc.202480901","url":null,"abstract":"<p><b>The Front Cover</b> presents a nanohybrid system consisting of the photocatalyst TiO<sub>2</sub>, photothermal gold nanoparticles, and thermo-responsive poly-<i>N</i>-isopropylacrylamide (TiO<sub>2</sub>-Au-PNM). This system combines the photothermal-controlled cargo release, triggered by visible-light irradiation, mediated by lower critical solution temperature (LCST) and by photothermal conversion effect, with the excellent photocatalytic effect prompted by UVB-light excitation. More information can be found in the Research Article by Salvatore Petralia and co-workers (DOI 10.1002/cptc.202400088).<figure>\u0000 <div><picture>\u0000 <source></source></picture><p></p>\u0000 </div>\u0000 </figure>\u0000 </p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"8 9","pages":""},"PeriodicalIF":3.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cptc.202480901","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142170084","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}
ChemPhotoChemPub Date : 2024-09-07DOI: 10.1002/cptc.202400260
Satish Kumar Singh, Vishwa K. Patel, Divyani P. Patel
{"title":"Harmonizing Visible‐Light in Green Synthesis: Unrevealing the Brilliance of Metal‐Free Cross‐Coupling of Unsaturated Hydrocarbons for C–C Bonds Formation","authors":"Satish Kumar Singh, Vishwa K. Patel, Divyani P. Patel","doi":"10.1002/cptc.202400260","DOIUrl":"https://doi.org/10.1002/cptc.202400260","url":null,"abstract":"Visible‐light induced, photoredox catalysis has opened a wide range in the transformation of organic compounds in recent times. In synthetic organic chemistry HAT (hydrogen atom transfer) and SET (single electron transfer) mechanisms are a very noteworthy routes that has opened a window in favor of C‐C single bond formations. Usually, a major role of unsaturated hydrocarbons is to participate in carbon‐carbon bond formation as they carry reactive π‐bond. Under visible‐light, metal‐free cross‐coupling reactions are particularly favorable because of their atom economy, increased efficiency, and environmentally friendly procedures that result in the construction of C‐C bonds. The review emphasizes the latest advancements of visible‐light mediated, cross‐coupling reactions of unsaturated hydrocarbons in metal‐free conditions for constructing carbon‐carbon single bonds.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"82 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217782","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":"Synthesis of Diketopyrrolopyrrole Based Photoactive Materials via Photoredox C‐H Activation","authors":"Vinay Kumar, Bommaramoni Yadagiri, Surya Prakash Singh","doi":"10.1002/cptc.202400069","DOIUrl":"https://doi.org/10.1002/cptc.202400069","url":null,"abstract":"The synthesis of diketopyrrolopyrrole (DPP) derivatives followed the well‐known conventional cross‐coupling methods such as Suzuki, Stille, Sonogashira, and Negishi cross‐coupling reactions. However, these methods required unfavorable reaction conditions, organometallic precursors, and high temperatures. In addition, the synthesis of conventional cross‐coupling partners including organoboranes, stannane, and acetylenes required drastic reaction conditions and strong bases. In this work, a wide variety of thiophene‐diketopyrrolopyrrole (TDPP)‐based semiconducting materials (36 compounds) were synthesized via Pd‐catalysed photoredox methodology by using N‐hydroxyphthalimide (NHP) based coupling partners, which can be readily prepared from N‐hydroxyphthalimide and carboxylic acid or aldehyde derivatives via single step C‐O bond formation reactions with good yield (80‐90%). This methodology minimizes additional synthetic steps, harsh reaction conditions, and high temperature (100‐150 oC). Optoelectronic studies suggest that the synthesized materials have suitable band gap, HOMO and LUMO levels for variety of optoelectronic applications. To the best of our knowledge, this is the first report on the synthesis of TDPP‐based π‐conjugated materials via the photoredox method.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"319 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142227249","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}
ChemPhotoChemPub Date : 2024-08-30DOI: 10.1002/cptc.202400137
Bharat A. Maru, Vandana J. Rao, Sanjeev R. Kane, U. K. Goutam, Chetan K. Modi
{"title":"Green Protocol For Synthesis of Cu2O@g‐C3N4 Photocatalysts For 1, 4 Radical Oxidative Addition of Trans Crotonaldehyde Under Visible Light Condition","authors":"Bharat A. Maru, Vandana J. Rao, Sanjeev R. Kane, U. K. Goutam, Chetan K. Modi","doi":"10.1002/cptc.202400137","DOIUrl":"https://doi.org/10.1002/cptc.202400137","url":null,"abstract":"Using visible light conditions, we have developed a green protocol to prepare copper oxide‐doped graphitic carbon nitride (Cu2O@g‐C3N4) photocatalysts with varied ratios of g‐C3N4 nanosheets to copper oxide‐dopant (0.1%, 0.5%, 0.7%, and 5% respectively) and characterized through various physicochemical techniques. These photo‐responsive catalysts were used for the 1,4 radical oxidative addition of trans crotonaldehyde into β‐hydroxybutyric acid (BA) as a major product, utilizing 30% hydrogen peroxide as an oxidant and a white LED (Light Emitting Diode) source. Under the innoculous eco‐friendly stipulations, Cu2O@g‐C3N4 (5%) exclusively promoted the aforementioned reaction leading to 99.85% trans crotonaldehyde conversion with 67.57%, 24.1%, and 9.1% selectivity for β‐hydroxybutyric acid, crotonic acid and subsequent radical synthesis, respectively.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"6 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217784","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}
ChemPhotoChemPub Date : 2024-08-29DOI: 10.1002/cptc.202400221
Xiaobing Liu, Zhixiong Cai, Qingxiang Wang
{"title":"Thermally Activated Delayed Fluorescence Emitters for Efficient Electrochemiluminescence","authors":"Xiaobing Liu, Zhixiong Cai, Qingxiang Wang","doi":"10.1002/cptc.202400221","DOIUrl":"https://doi.org/10.1002/cptc.202400221","url":null,"abstract":"Thermally activated delayed fluorescence (TADF) materials have attracted considerable interest due to their ability to enhance electrochemiluminescence (ECL). This is achieved through the efficient upconversion of triplet excitons and the subsequent radiative transitions. However, despite the potential of TADF materials, there have been few studies exploring their application in ECL field. Accordingly, in this concept, a number of TADF materials, which can be categorized into two principal groups based on intramolecular bond charge transfer and intermolecular space charge transfer, are introduced in order to explore the potential for their application in ECL. A brief review of their properties not only helps to deepen the understanding of the nature of TADF materials, but also provides basic guidance and support for the introduction of the TADF mechanism into ECL systems, with the aim of enhancing the luminescence efficiency of ECL.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"60 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142217785","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}
ChemPhotoChemPub Date : 2024-08-26DOI: 10.1002/cptc.202400246
Yilin Xue, Duobin Chao
{"title":"Organic and Non‐Precious Metal Photosensitizers for Photocatalytic CO2 Reduction","authors":"Yilin Xue, Duobin Chao","doi":"10.1002/cptc.202400246","DOIUrl":"https://doi.org/10.1002/cptc.202400246","url":null,"abstract":"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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"59 1","pages":""},"PeriodicalIF":3.7,"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}
{"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 Shanmugasundram, Kannan Vellaisamy, Nithesh Kumar Krishnan, Murali Krishnan Mani, Selvam Kaliyamoorthy, Bo-Tau Liu, Stalin Thambusamy","doi":"10.1002/cptc.202400170","DOIUrl":"https://doi.org/10.1002/cptc.202400170","url":null,"abstract":"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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"26 1","pages":""},"PeriodicalIF":3.7,"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}
ChemPhotoChemPub Date : 2024-08-23DOI: 10.1002/cptc.202400216
Baldeep K Sidhu, Issiah B Lozada, Rathiesh Pandian, Ibrahim Alfurayj, Clemens Burda, David E. Herbert
{"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":"https://doi.org/10.1002/cptc.202400216","url":null,"abstract":"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.","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"12 1","pages":""},"PeriodicalIF":3.7,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}