Abstract Thermally activated delayed fluorescence (TADF)-sensitized fluorescence is a promising strategy to maintain the advantage of TADF materials and fluorescent materials. Nevertheless, the delayed lifetime of the TADF sensitizer is still relatively long, which causes heavy efficiency roll-off. Here we reported a valid tactic to construct fluorescent devices with low-efficiency roll-off by utilizing the TADF sensitizer with a reduced delayed lifetime. By the construction of the sensitization system, the energy transfer efficiency can reach up to 90%. The high-energy transfer efficiency and the TADFʼs short delayed lifetime result in high sensitization over 95% and the maximum external quantum efficiency of 16.2%. Meanwhile, the TADF-sensitized fluorescent devices exhibit reduced efficiency roll-off with an “onset” current density of 23 mA · cm−2. Our results provide an effective strategy to reduce the efficiency roll-off of the TADF sensitization system.
{"title":"Sensitized Fluorescence Organic Light-Emitting Diodes with Reduced Efficiency Roll-Off","authors":"Zhi-yi Li, Ruifang Wang, Yangyang Zeng, Xiangyun Dong, Guanhao Liu, Xiaoxiao Hu, Teng Gao, Honglei Gao, Yuanyuan Qin, Xiuxian Gu, Chun‐Sing Lee, Jiguang Liu, Pengfei Wang, Ying Wang","doi":"10.1055/a-1711-5768","DOIUrl":"https://doi.org/10.1055/a-1711-5768","url":null,"abstract":"Abstract Thermally activated delayed fluorescence (TADF)-sensitized fluorescence is a promising strategy to maintain the advantage of TADF materials and fluorescent materials. Nevertheless, the delayed lifetime of the TADF sensitizer is still relatively long, which causes heavy efficiency roll-off. Here we reported a valid tactic to construct fluorescent devices with low-efficiency roll-off by utilizing the TADF sensitizer with a reduced delayed lifetime. By the construction of the sensitization system, the energy transfer efficiency can reach up to 90%. The high-energy transfer efficiency and the TADFʼs short delayed lifetime result in high sensitization over 95% and the maximum external quantum efficiency of 16.2%. Meanwhile, the TADF-sensitized fluorescent devices exhibit reduced efficiency roll-off with an “onset” current density of 23 mA · cm−2. Our results provide an effective strategy to reduce the efficiency roll-off of the TADF sensitization system.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"3 1","pages":"488 - 492"},"PeriodicalIF":0.0,"publicationDate":"2021-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48166025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract All-organic thermally activated delayed fluorescence (TADF) materials have emerged as potential candidates for optoelectronic devices and biomedical applications. However, the development of organic TADF probes with strong emission in the longer wavelength region (> 600 nm) remains a challenge. Strong π-conjugated rigid acceptor cores substituted with multiple donor units can be a viable design strategy to obtain red TADF probes. Herein, 3,6-di-t-butyl carbazole substituted to a dibenzopyridoquinoxaline acceptor core resulted in a T-shaped donor–acceptor–donor compound, PQACz-T, exhibiting red TADF in polymer-embedded thin-films. Further, PQACz-T self-assembled to molecular nanoaggregates of diverse size and shape in THF–water mixture showing bright red emission along with delayed fluorescence even in an aqueous environment. The self-assembly and the excited-state properties of PQACz-T were compared with the nonalkylated analogue, PQCz-T. The delayed fluorescence in nanoaggregates was attributed to the high rate of reverse intersystem crossing. Moreover, an aqueous dispersion of the smaller-sized, homogeneous distribution of fluorescent nanoparticles was fabricated upon encapsulating PQACz-T in a triblock copolymer, F-127. Cytocompatible polymer-encapsulated PQACz-T nanoparticles with large Stokes shift and excellent photostability were demonstrated for the specific imaging of lipid droplets in HeLa cells.
{"title":"Red Thermally Activated Delayed Fluorescence in Dibenzopyridoquinoxaline-Based Nanoaggregates","authors":"Subhadeep Das, Subhankar Kundu, Bahadur Sk, Md. Sujahangir Kabir Sarkar, Abhijit Patra","doi":"10.1055/a-1679-9558","DOIUrl":"https://doi.org/10.1055/a-1679-9558","url":null,"abstract":"Abstract All-organic thermally activated delayed fluorescence (TADF) materials have emerged as potential candidates for optoelectronic devices and biomedical applications. However, the development of organic TADF probes with strong emission in the longer wavelength region (> 600 nm) remains a challenge. Strong π-conjugated rigid acceptor cores substituted with multiple donor units can be a viable design strategy to obtain red TADF probes. Herein, 3,6-di-t-butyl carbazole substituted to a dibenzopyridoquinoxaline acceptor core resulted in a T-shaped donor–acceptor–donor compound, PQACz-T, exhibiting red TADF in polymer-embedded thin-films. Further, PQACz-T self-assembled to molecular nanoaggregates of diverse size and shape in THF–water mixture showing bright red emission along with delayed fluorescence even in an aqueous environment. The self-assembly and the excited-state properties of PQACz-T were compared with the nonalkylated analogue, PQCz-T. The delayed fluorescence in nanoaggregates was attributed to the high rate of reverse intersystem crossing. Moreover, an aqueous dispersion of the smaller-sized, homogeneous distribution of fluorescent nanoparticles was fabricated upon encapsulating PQACz-T in a triblock copolymer, F-127. Cytocompatible polymer-encapsulated PQACz-T nanoparticles with large Stokes shift and excellent photostability were demonstrated for the specific imaging of lipid droplets in HeLa cells.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"3 1","pages":"477 - 487"},"PeriodicalIF":0.0,"publicationDate":"2021-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42828005","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract The development of n-type semiconductors lags far behind that of their p-type counterparts, demonstrating the exploration of exclusive n-type π-conjugated polymers is significant. The double B←N-bridged bipyridine (BNBP)-based polymers P-BNBP-TVT containing (E)-1,2-di(thiophen-2-yl)ethene (TVT) previously reported exhibits ambipolar character because of the electron-rich nature. Herein, we incorporated strong electron-withdrawing cyano groups into the 3,3′-positions of the TVT moiety to a copolymer P-BNBP-2CNTVT to develop n-type π-conjugated polymers. The LUMO/HOMO energy levels of P-BNBP-2CNTVT are −3.80/−5.95 eV, respectively, which are ~0.4 eV lower than that of P-BNBP-TVT without cyano groups. Unsurprisingly, compared with ambipolar P-BNBP-TVT, the organic field-effect transistors (OFETs) based on P-BNBP-2CNTVT showed unipolar n-type characteristics with an electron mobility of 0.026 cm2 · V−1 · s−1 and a lower threshold voltage of ~25 V as well as high I on/I off of ~105. This study demonstrates that organoboron π-conjugated polymers could be regarded as a tool for constructing exclusive n-type semiconducting polymers used in OFETs.
n型半导体的发展远远落后于p型半导体，这表明探索n型π共轭聚合物具有重要意义。先前报道的含有(E)-1,2-二(噻吩-2-基)乙烯(TVT)的双B←n桥联吡啶(BNBP)基聚合物P-BNBP-TVT由于富电子性质而具有双极性特征。本文将强吸电子氰基引入到共聚物P-BNBP-2CNTVT的3,3 '位，制备了n型π共轭聚合物。P-BNBP-2CNTVT的LUMO/HOMO能级分别为−3.80/−5.95 eV，比不含氰基的P-BNBP-TVT低~0.4 eV。不出所料，与双极性P-BNBP-TVT相比，基于P-BNBP-2CNTVT的有机场效应晶体管(ofet)表现出单极n型特性，电子迁移率为0.026 cm2·V−1·s−1，阈值电压较低，为~25 V, I /I关高，为~105。该研究表明，有机硼π共轭聚合物可以作为构建专用于ofet的n型半导体聚合物的工具。
{"title":"Incorporating Cyano Groups to a Conjugated Polymer Based on Double B←N-Bridged Bipyridine Units for Unipolar n-Type Organic Field-Effect Transistors","authors":"Xumin Cao, Yang Min, H. Tian, Jun Liu","doi":"10.1055/a-1639-2383","DOIUrl":"https://doi.org/10.1055/a-1639-2383","url":null,"abstract":"Abstract The development of n-type semiconductors lags far behind that of their p-type counterparts, demonstrating the exploration of exclusive n-type π-conjugated polymers is significant. The double B←N-bridged bipyridine (BNBP)-based polymers P-BNBP-TVT containing (E)-1,2-di(thiophen-2-yl)ethene (TVT) previously reported exhibits ambipolar character because of the electron-rich nature. Herein, we incorporated strong electron-withdrawing cyano groups into the 3,3′-positions of the TVT moiety to a copolymer P-BNBP-2CNTVT to develop n-type π-conjugated polymers. The LUMO/HOMO energy levels of P-BNBP-2CNTVT are −3.80/−5.95 eV, respectively, which are ~0.4 eV lower than that of P-BNBP-TVT without cyano groups. Unsurprisingly, compared with ambipolar P-BNBP-TVT, the organic field-effect transistors (OFETs) based on P-BNBP-2CNTVT showed unipolar n-type characteristics with an electron mobility of 0.026 cm2 · V−1 · s−1 and a lower threshold voltage of ~25 V as well as high I on/I off of ~105. This study demonstrates that organoboron π-conjugated polymers could be regarded as a tool for constructing exclusive n-type semiconducting polymers used in OFETs.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"3 1","pages":"469 - 476"},"PeriodicalIF":0.0,"publicationDate":"2021-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48559069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Exciton dynamics in organic semiconductors is a subject of great significance from the standpoint of light emission, as well as light harvesting. As transient excited state species, excimers are expected to play a significant role in the dynamics and the fate of the excited state. Till recently, the discourse on excimers in organic systems revolved around their role in aggregation-induced fluorescence quenching, or utilizing their characteristic red-shifted emission to report local interactions. But in the last decade, research in the area of organic multichromophoric systems has brought the spotlight back on this fascinating species. This review focuses on recent developments that highlight the importance of excimers in various processes involving multichromophoric systems, such as circularly polarized emission, exciton migration, and singlet fission. The review also attempts to address the question of whether excimers are useful or detrimental to various photophysical and photochemical processes of importance. Table of content: Introduction Excimers in Multichromophoric Assemblies Excimer Luminescence Excimers in Light Harvesting Conclusions and Outlook
{"title":"Excimers in Multichromophoric Assemblies: Boon or Bane?","authors":"Debangshu Chaudhuri","doi":"10.1055/a-1578-0960","DOIUrl":"https://doi.org/10.1055/a-1578-0960","url":null,"abstract":"Abstract Exciton dynamics in organic semiconductors is a subject of great significance from the standpoint of light emission, as well as light harvesting. As transient excited state species, excimers are expected to play a significant role in the dynamics and the fate of the excited state. Till recently, the discourse on excimers in organic systems revolved around their role in aggregation-induced fluorescence quenching, or utilizing their characteristic red-shifted emission to report local interactions. But in the last decade, research in the area of organic multichromophoric systems has brought the spotlight back on this fascinating species. This review focuses on recent developments that highlight the importance of excimers in various processes involving multichromophoric systems, such as circularly polarized emission, exciton migration, and singlet fission. The review also attempts to address the question of whether excimers are useful or detrimental to various photophysical and photochemical processes of importance. Table of content: Introduction Excimers in Multichromophoric Assemblies Excimer Luminescence Excimers in Light Harvesting Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"3 1","pages":"455 - 468"},"PeriodicalIF":0.0,"publicationDate":"2021-08-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1578-0960","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47043724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rupam Roy, A. Khan, Oendrila Chatterjee, S. Bhunia, A. Koner
Abstract Perylene dyes have transcended their role as simple colorants and have been reinvigorated as functional dyes. Based on the substitution at the peri-position by six-membered carboxylic imides, the perylene family is principally embellished with perylene diimides (PDIs) and perylene monoimides (PMIs). Perylene dyes are widely acclaimed and adorned on account of their phenomenal thermal, chemical, and photostability juxtaposed with their high absorption coefficient and near-unity fluorescence quantum yield. Although symmetric PDIs have always been in the limelight, their asymmetrical counterpart PMI is already rubbing shoulders, thanks to the consistent efforts of several scientific minds. Recently, there has been an upsurge in engendering PMI-based versatile organic architectures decked with intriguing photophysical properties and pertinent applications. In this review, the synthesis and photophysical features of various PMI-based derivatives along with their relevant applications in the arena of organic photovoltaics, photocatalysis, self-assembly, fluorescence sensing, and bio-imaging are accrued and expounded, hoping to enlighten the less delved but engrossing realm of PMIs. Table of content: 1 Introduction 2 Advantages of PMI over PDI 3 Challenges in Working with PMI and Ways to Overcome 4 Various Aspects of Reactivity of Different Positions 5 Synthesis of the PMI core 6 Synthesis of PMI Derivatives 6.1 Bromination of PMI 6.2 Synthesis of PMI Derivatives using Coupling Reactions 6.2.1 Suzuki Coupling 6.2.2 Sonogashira Coupling 6.2.3 Buchwald–Hartwig Coupling Reaction 6.3 Nucleophilic Substitution Reactions 6.4 Peri-Annulation Reaction 7 Photophysical Properties of PMI 8 Singlet Fission Properties 9 Förster Resonance Energy Transfer with PMI 10 Symmetry Breaking Charge Transfer Properties 11 Panchromatic Light Absorption Properties of PMI 12 Acid/Base Sensitivity of PMI 13 NIR-Absorbing PMI 14 Achieving of Triplet State Using PMI 15 Solid-State Emissive PMI 16 Thermo-Responsive Materials with PMI 17 Photo-Responsive PMI Derivatives 18 Electrochemical Properties of Rylene Derivative 19 Self-Assembling Properties of PMI Derivatives 20 Applications of PMI in Solar Cells 21 PMIs in Bulk Heterojunction Solar Cells 22 PMIs in Dye-Sensitized Solar Cells 23 PMI as a Fluorescent Reporter 23.1 Application of PMI Derivatives for Bio-Imaging 23.2 Hydrophilic PMIs for Bio-Imaging 23.3 Aggregated PMI as NIR-Emissive Fluoroprobe for Bio-Imaging 24 Photocatalytic Hydrogen Generation using PMI 25 PMI-Based Organocatalysis 26 PMI Derivatives for Single-molecule Spectroscopy 27 Host–Guest Chemistry with PMI 28 Conclusions and Outlook
{"title":"Perylene Monoimide as a Versatile Fluoroprobe: The Past, Present, and Future","authors":"Rupam Roy, A. Khan, Oendrila Chatterjee, S. Bhunia, A. Koner","doi":"10.1055/a-1551-6930","DOIUrl":"https://doi.org/10.1055/a-1551-6930","url":null,"abstract":"Abstract Perylene dyes have transcended their role as simple colorants and have been reinvigorated as functional dyes. Based on the substitution at the peri-position by six-membered carboxylic imides, the perylene family is principally embellished with perylene diimides (PDIs) and perylene monoimides (PMIs). Perylene dyes are widely acclaimed and adorned on account of their phenomenal thermal, chemical, and photostability juxtaposed with their high absorption coefficient and near-unity fluorescence quantum yield. Although symmetric PDIs have always been in the limelight, their asymmetrical counterpart PMI is already rubbing shoulders, thanks to the consistent efforts of several scientific minds. Recently, there has been an upsurge in engendering PMI-based versatile organic architectures decked with intriguing photophysical properties and pertinent applications. In this review, the synthesis and photophysical features of various PMI-based derivatives along with their relevant applications in the arena of organic photovoltaics, photocatalysis, self-assembly, fluorescence sensing, and bio-imaging are accrued and expounded, hoping to enlighten the less delved but engrossing realm of PMIs. Table of content: 1 Introduction 2 Advantages of PMI over PDI 3 Challenges in Working with PMI and Ways to Overcome 4 Various Aspects of Reactivity of Different Positions 5 Synthesis of the PMI core 6 Synthesis of PMI Derivatives 6.1 Bromination of PMI 6.2 Synthesis of PMI Derivatives using Coupling Reactions 6.2.1 Suzuki Coupling 6.2.2 Sonogashira Coupling 6.2.3 Buchwald–Hartwig Coupling Reaction 6.3 Nucleophilic Substitution Reactions 6.4 Peri-Annulation Reaction 7 Photophysical Properties of PMI 8 Singlet Fission Properties 9 Förster Resonance Energy Transfer with PMI 10 Symmetry Breaking Charge Transfer Properties 11 Panchromatic Light Absorption Properties of PMI 12 Acid/Base Sensitivity of PMI 13 NIR-Absorbing PMI 14 Achieving of Triplet State Using PMI 15 Solid-State Emissive PMI 16 Thermo-Responsive Materials with PMI 17 Photo-Responsive PMI Derivatives 18 Electrochemical Properties of Rylene Derivative 19 Self-Assembling Properties of PMI Derivatives 20 Applications of PMI in Solar Cells 21 PMIs in Bulk Heterojunction Solar Cells 22 PMIs in Dye-Sensitized Solar Cells 23 PMI as a Fluorescent Reporter 23.1 Application of PMI Derivatives for Bio-Imaging 23.2 Hydrophilic PMIs for Bio-Imaging 23.3 Aggregated PMI as NIR-Emissive Fluoroprobe for Bio-Imaging 24 Photocatalytic Hydrogen Generation using PMI 25 PMI-Based Organocatalysis 26 PMI Derivatives for Single-molecule Spectroscopy 27 Host–Guest Chemistry with PMI 28 Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"3 1","pages":"417 - 454"},"PeriodicalIF":0.0,"publicationDate":"2021-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1551-6930","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44022375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Naphthalene-diimide (NDI)-derived building blocks have been explored extensively for supramolecular assembly as they exhibit attractive photophysical properties, suitable for applications in organic optoelectronics. Core-substituted derivatives of the NDI chromophore (cNDI) differ significantly from the parent NDI dye in terms of optical and redox properties. Adequate molecular engineering opportunities and substitution-dependent tunable optoelectronic properties make cNDI derivatives highly promising candidates for supramolecular assembly and functional materials. This short review discusses recent development in the area of functional supramolecular assemblies based on cNDIs and related molecules. Table of contents 1. Introduction 2. General Supramolecular Assemblies of cNDI Derivatives 3. cNDI-Based Chiral Supramolecular Assemblies and Functional Materials 4. Controlled Supramolecular Polymerization with cNDI Derivatives 5. Dimeric Naphthalimide-Based Building Blocks 6. Conclusions and Outlook
{"title":"Core-Substituted Naphthalene-Diimides (cNDI) and Related Derivatives: Versatile Scaffold for Supramolecular Assembly and Functional Materials","authors":"Anurag Mukherjee, Suhrit Ghosh","doi":"10.1055/a-1530-0476","DOIUrl":"https://doi.org/10.1055/a-1530-0476","url":null,"abstract":"Abstract Naphthalene-diimide (NDI)-derived building blocks have been explored extensively for supramolecular assembly as they exhibit attractive photophysical properties, suitable for applications in organic optoelectronics. Core-substituted derivatives of the NDI chromophore (cNDI) differ significantly from the parent NDI dye in terms of optical and redox properties. Adequate molecular engineering opportunities and substitution-dependent tunable optoelectronic properties make cNDI derivatives highly promising candidates for supramolecular assembly and functional materials. This short review discusses recent development in the area of functional supramolecular assemblies based on cNDIs and related molecules. Table of contents 1. Introduction 2. General Supramolecular Assemblies of cNDI Derivatives 3. cNDI-Based Chiral Supramolecular Assemblies and Functional Materials 4. Controlled Supramolecular Polymerization with cNDI Derivatives 5. Dimeric Naphthalimide-Based Building Blocks 6. Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"405 - 416"},"PeriodicalIF":0.0,"publicationDate":"2021-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1530-0476","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49274259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yusuke Ishigaki, Kota Asai, Takuya Shimajiri, T. Akutagawa, T. Fukushima, Takanori Suzuki
Abstract The crystal structures of a series of tetracyanonaphthoquinodimethanes fused with a selenadiazole or thiadiazole ring revealed that their molecular packing is determined mainly by two intermolecular interactions: chalcogen bond (ChB) and weak hydrogen bond (WHB). ChB between Se and a cyano group dictates the packing of selenadiazole derivatives, whereas the S-based ChB is much weaker and competes with WHB in thiadiazole analogues. This difference can be explained by different electrostatic potentials as revealed by density functional theory calculations. A proper molecular design that weakens WHB can change the contribution of ChB in determining the crystal packing of thiadiazole derivatives.
{"title":"Chalcogen Bond versus Weak Hydrogen Bond: Changing Contributions in Determining the Crystal Packing of [1,2,5]-Chalcogenadiazole-Fused Tetracyanonaphthoquinodimethanes","authors":"Yusuke Ishigaki, Kota Asai, Takuya Shimajiri, T. Akutagawa, T. Fukushima, Takanori Suzuki","doi":"10.1055/S-0041-1725046","DOIUrl":"https://doi.org/10.1055/S-0041-1725046","url":null,"abstract":"Abstract The crystal structures of a series of tetracyanonaphthoquinodimethanes fused with a selenadiazole or thiadiazole ring revealed that their molecular packing is determined mainly by two intermolecular interactions: chalcogen bond (ChB) and weak hydrogen bond (WHB). ChB between Se and a cyano group dictates the packing of selenadiazole derivatives, whereas the S-based ChB is much weaker and competes with WHB in thiadiazole analogues. This difference can be explained by different electrostatic potentials as revealed by density functional theory calculations. A proper molecular design that weakens WHB can change the contribution of ChB in determining the crystal packing of thiadiazole derivatives.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"58 1","pages":"090 - 096"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/S-0041-1725046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"58140423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Akira Shinohara, Zhenfeng Guo, C. Pan, T. Nakanishi
Abstract Solvent-free fluidic materials possessing optoelectronic functions are expected to be major components in soft electronics applications. Conjugated polymers are promising targets for this purpose and their design approaches are classified into three types with respect to their structure: conjugation breaking (Type I), copolymerization with flexible polymers (Type II), and side chain engineering (Type III). In this short review, we highlight several early attempts to produce Type III conjugated polymers. We also present fully characterized Type III fluids recently developed by our group, with a brief summary of the structure–property relationship and fluidity-oriented functions. Introduction 1 Polymer Design 1.1 Fluidity of Polymeric Materials 1.2 Type III CPs with T g < 25 °C 1.3 Fluidification of Polyfluorenes 1.4 Effect of Side Chain Length 2 Fluidity-Oriented Functions 2.1 Mechanofluorochromism 2.2 Consistent Luminescence in Wide Range of Elastic Moduli 2.3 Prediction of Viscoelasticity Conclusions and Outlook
{"title":"Solvent-Free Conjugated Polymer Fluids with Optical Functions","authors":"Akira Shinohara, Zhenfeng Guo, C. Pan, T. Nakanishi","doi":"10.1055/a-1491-4818","DOIUrl":"https://doi.org/10.1055/a-1491-4818","url":null,"abstract":"Abstract Solvent-free fluidic materials possessing optoelectronic functions are expected to be major components in soft electronics applications. Conjugated polymers are promising targets for this purpose and their design approaches are classified into three types with respect to their structure: conjugation breaking (Type I), copolymerization with flexible polymers (Type II), and side chain engineering (Type III). In this short review, we highlight several early attempts to produce Type III conjugated polymers. We also present fully characterized Type III fluids recently developed by our group, with a brief summary of the structure–property relationship and fluidity-oriented functions. Introduction 1 Polymer Design 1.1 Fluidity of Polymeric Materials 1.2 Type III CPs with T g < 25 °C 1.3 Fluidification of Polyfluorenes 1.4 Effect of Side Chain Length 2 Fluidity-Oriented Functions 2.1 Mechanofluorochromism 2.2 Consistent Luminescence in Wide Range of Elastic Moduli 2.3 Prediction of Viscoelasticity Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"309 - 320"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1491-4818","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"48970046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Isabell S. Geisler, M. Forster, Bujamin Misimi, Jakob Schedlbauer, T. Riedl, J. Lupton, U. Scherf
Abstract A fully soluble poly(9,10-anthrylene ethynylene), poly[2,6-(2-octyldecyl)-9,10-anthrylene ethynylene] PAAE, with moderate degrees of polymerization Pn of ca. 10 is generated in a reductive, dehalogenative homocoupling scheme, starting from a 2,6-dialkylated 9,10-bis(dibromomethylene)-9,10-dihydroanthracene monomer and n-BuLi/CuCN as the reducing agent. PAAE shows surprisingly broad and unstructured absorption and photoluminescence emission bands with peaks at 506 nm and 611 nm, respectively, both in chloroform solution. The long absorption tail ranging into the 600–700 nm region and the large Stokes shift points to a high degree of geometrical disorder in the arrangement of the 9,10-anthrylene chromophores along the distorted polymer backbone. This disorder is borne out in the unusually strong wavelength dependence of fluorescence depolarisation, both with regards to the excitation and the emission wavelengths. Picosecond fluorescence depolarisation spectroscopy provides clear evidence for the presence of orthogonal transition dipole moments, presumably arising from the off-axis transition of the anthracene unit and the on-axis transition of the polymer backbone. Intramolecular energy relaxation then gives rise to the observed fluorescence depolarization dynamics.
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Abstract This review summarizes syntheses of S,N-heteropentacenes, i.e. electron-rich sulfur and nitrogen-embedding pentacycles, and briefly highlights selected applications in molecular electronics. Depending on the anellation mode and the number of incorporated heteroatoms, electron density can be raised by increasing nitrogen incorporation and polarizability is manifested by the sulfur content. In comparison to triacene analogues, the conjugation pathways of S,N-heteropentacenes are increased and the favorable acene-typical crystallization behavior allows for diverse application in organic electronics. Furthermore, substitution patterns allow fine-tuning the electronic properties, extending the π-systems, and supplying structural elements for further application. 1 Introduction 2 Thiophene-Centered S,N-Heteropentacenes 2.1 Dipyrrolo-Fused Thiophenes 2.2 Diindolo-Fused Thiophenes 3 Pyrrole-Centered S,N-Heteropentacenes 3.1 Dithieno-Fused Pyrroles 3.2 Bis[1]benzothieno-Fused Pyrrole 4 Fused 1,4-Thiazines 4.1 Dinaphtho-Fused 1,4-Thiazines 4.2 Bis[1]benzothieno-Fused 1,4-Thiazines 5 Conclusions and Outlook
摘要本文综述了S, n-杂戊烯类化合物的合成方法，即富电子的含硫和含氮五环化合物，并简要介绍了它们在分子电子学中的应用。根据膜化模式和杂原子掺入数的不同，通过增加氮的掺入可以提高电子密度，而极化性则通过硫含量来体现。与三烯类似物相比，S, n -杂戊烯的缀合途径增加，良好的典型三烯结晶行为允许在有机电子学中的多种应用。此外，取代模式允许微调电子性质，扩展π-体系，并为进一步应用提供结构元素。2以噻吩为中心的S, n -杂戊烯类化合物2.1二吡咯-融合噻吩类化合物2.2二吲哚-融合噻吩类化合物3以吡咯为中心的S, n -杂戊烯类化合物3.1二噻吩-融合吡咯类化合物3.2双苯并噻吩-融合吡咯类化合物4融合1,4-噻吩类化合物4.1二萘-融合1,4-噻吩类化合物4.2双苯并噻吩-融合1,4-噻吩类化合物5结论与展望
{"title":"S,N-Heteropentacenes – Syntheses of Electron-Rich Anellated Pentacycles","authors":"Henning R V Berens, T. Müller","doi":"10.1055/s-0041-1726450","DOIUrl":"https://doi.org/10.1055/s-0041-1726450","url":null,"abstract":"Abstract This review summarizes syntheses of S,N-heteropentacenes, i.e. electron-rich sulfur and nitrogen-embedding pentacycles, and briefly highlights selected applications in molecular electronics. Depending on the anellation mode and the number of incorporated heteroatoms, electron density can be raised by increasing nitrogen incorporation and polarizability is manifested by the sulfur content. In comparison to triacene analogues, the conjugation pathways of S,N-heteropentacenes are increased and the favorable acene-typical crystallization behavior allows for diverse application in organic electronics. Furthermore, substitution patterns allow fine-tuning the electronic properties, extending the π-systems, and supplying structural elements for further application. 1 Introduction 2 Thiophene-Centered S,N-Heteropentacenes 2.1 Dipyrrolo-Fused Thiophenes 2.2 Diindolo-Fused Thiophenes 3 Pyrrole-Centered S,N-Heteropentacenes 3.1 Dithieno-Fused Pyrroles 3.2 Bis[1]benzothieno-Fused Pyrrole 4 Fused 1,4-Thiazines 4.1 Dinaphtho-Fused 1,4-Thiazines 4.2 Bis[1]benzothieno-Fused 1,4-Thiazines 5 Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"155 - 167"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/s-0041-1726450","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"43355101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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