T. Ashirov, Maymounah Alrayyani, K. Song, O. Miljanić, Ali Coskun
Abstract Porous organic polymers (POPs) incorporating macrocyclic units have been investigated in recent years in an effort to transfer macrocycles' intrinsic host–guest properties onto the porous networks to achieve complex separations. In this regard, highly interesting building blocks are presented by the family of cyclotetrabenzoin macrocycles with rigid, well-defined, electron-deficient cavities. This macrocycle shows high affinity towards linear guest molecules such as carbon dioxide, thus offering an ideal building block for the synthesis of CO2-philic POPs. Herein, we report the synthesis of a POP through the condensation reaction between cyclotetrabenzil and 1,2,4,5-tetraaminobenzene under ionothermal conditions using the eutectic zinc chloride/sodium chloride/potassium chloride salt mixture at 250 °C. Notably, following the condensation reaction, the macrocycle favors three-dimensional (3D) growth rather than a two-dimensional one while retaining the cavity. The resulting polymer, named 3D-mPOP, showed a highly microporous structure with a BET surface area of 1142 m2 g−1 and a high carbon dioxide affinity with a binding enthalpy of 39 kJ mol−1. Moreover, 3D-mPOP showed very high selectivity for carbon dioxide in carbon dioxide/methane and carbon dioxide/nitrogen mixtures.
{"title":"Cyclotetrabenzil-Based Porous Organic Polymers with High Carbon Dioxide Affinity","authors":"T. Ashirov, Maymounah Alrayyani, K. Song, O. Miljanić, Ali Coskun","doi":"10.1055/a-1512-5753","DOIUrl":"https://doi.org/10.1055/a-1512-5753","url":null,"abstract":"Abstract Porous organic polymers (POPs) incorporating macrocyclic units have been investigated in recent years in an effort to transfer macrocycles' intrinsic host–guest properties onto the porous networks to achieve complex separations. In this regard, highly interesting building blocks are presented by the family of cyclotetrabenzoin macrocycles with rigid, well-defined, electron-deficient cavities. This macrocycle shows high affinity towards linear guest molecules such as carbon dioxide, thus offering an ideal building block for the synthesis of CO2-philic POPs. Herein, we report the synthesis of a POP through the condensation reaction between cyclotetrabenzil and 1,2,4,5-tetraaminobenzene under ionothermal conditions using the eutectic zinc chloride/sodium chloride/potassium chloride salt mixture at 250 °C. Notably, following the condensation reaction, the macrocycle favors three-dimensional (3D) growth rather than a two-dimensional one while retaining the cavity. The resulting polymer, named 3D-mPOP, showed a highly microporous structure with a BET surface area of 1142 m2 g−1 and a high carbon dioxide affinity with a binding enthalpy of 39 kJ mol−1. Moreover, 3D-mPOP showed very high selectivity for carbon dioxide in carbon dioxide/methane and carbon dioxide/nitrogen mixtures.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"346 - 352"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1512-5753","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44133713","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}
J. Chalker, M. Mann, Max J H Worthington, Louisa J. Esdaile
Abstract Inverse vulcanization is a process in which highly abundant and low-cost elemental sulfur is copolymerized with an unsaturated organic molecule such as a polyene. This process has provided a variety of useful materials with high sulfur content—typically 50% or greater in sulfur by mass. These materials have garnered increasing interest in research as sorbents for mercury, due to the high affinity of sulfur for mercury. In this review, the features of mercury sorbents made by inverse vulcanization are presented. Additionally, case studies are provided to illustrate the variety of polymer architectures accessible with this chemistry, the versatility of these materials in mercury remediation, and prospects for industrial use. 1 Introduction 2 Sulfur Polymers by Inverse Vulcanization 3 Sulfur Polymers as Mercury Sorbents 4 Increasing Surface Area to Improve Mercury Uptake 5 Crosslinker Considerations 6 Sorption of Different Forms of Mercury 7 Life-Cycle Management 8 Conclusions and Outlook
{"title":"Polymers Made by Inverse Vulcanization for Use as Mercury Sorbents","authors":"J. Chalker, M. Mann, Max J H Worthington, Louisa J. Esdaile","doi":"10.1055/a-1502-2611","DOIUrl":"https://doi.org/10.1055/a-1502-2611","url":null,"abstract":"Abstract Inverse vulcanization is a process in which highly abundant and low-cost elemental sulfur is copolymerized with an unsaturated organic molecule such as a polyene. This process has provided a variety of useful materials with high sulfur content—typically 50% or greater in sulfur by mass. These materials have garnered increasing interest in research as sorbents for mercury, due to the high affinity of sulfur for mercury. In this review, the features of mercury sorbents made by inverse vulcanization are presented. Additionally, case studies are provided to illustrate the variety of polymer architectures accessible with this chemistry, the versatility of these materials in mercury remediation, and prospects for industrial use. 1 Introduction 2 Sulfur Polymers by Inverse Vulcanization 3 Sulfur Polymers as Mercury Sorbents 4 Increasing Surface Area to Improve Mercury Uptake 5 Crosslinker Considerations 6 Sorption of Different Forms of Mercury 7 Life-Cycle Management 8 Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"362 - 373"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1502-2611","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"46541520","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}
Asmerom O. Weldeab, Cory T. Kornman, Lei Li, D. Starkenburg, Xueying Zhao, D. E. Fagnani, Sara J. Sadovy, S. Perry, J. Xue, R. K. Castellano
Abstract A series of simple ditopic hydrogen-bonding-capable molecules functionalized with 2,4-diamino-1,3,5-triazine (DAT), barbiturate (B), and phthalhydrazide (PH) on both termini of a 2,2′-bithiophene linker were designed and synthesized. The intrinsic electronic structures of the ditopic DAT, PH, and B molecules were investigated with ground-state density functional theory calculations. Their solution absorbance was investigated with UV-vis, where it was found that increasing size of R group substituents on the bithiophene linker resulted in a general blue-shift in solution absorbance maximum. The solid-state optical properties of ditopic DAT and B thin films were evaluated by UV-vis, and it was found that the solid-state absorbance was red-shifted with respect to solution absorbance in all cases. The three DAT molecules were vacuum-thermal-deposited onto Au(111) substrates and the morphologies were examined using scanning tunneling microscopy. (DAT-T)2 was observed to organize into six-membered rosettes on the surface, whereas (DAT-TMe)2 formed linear assemblies before and after thermal annealing. For (DAT-Toct)2 , an irregular arrangement was observed, while (B-TMe)2 showed several co-existent assembly patterns. The work presented here provides fundamental molecular–supramolecular relationships useful for semiconductive materials design based on ditopic hydrogen-bonding-capable building blocks.
{"title":"Structure–Assembly–Property Relationships of Simple Ditopic Hydrogen-Bonding-Capable π-Conjugated Oligomers","authors":"Asmerom O. Weldeab, Cory T. Kornman, Lei Li, D. Starkenburg, Xueying Zhao, D. E. Fagnani, Sara J. Sadovy, S. Perry, J. Xue, R. K. Castellano","doi":"10.1055/a-1534-1508","DOIUrl":"https://doi.org/10.1055/a-1534-1508","url":null,"abstract":"Abstract A series of simple ditopic hydrogen-bonding-capable molecules functionalized with 2,4-diamino-1,3,5-triazine (DAT), barbiturate (B), and phthalhydrazide (PH) on both termini of a 2,2′-bithiophene linker were designed and synthesized. The intrinsic electronic structures of the ditopic DAT, PH, and B molecules were investigated with ground-state density functional theory calculations. Their solution absorbance was investigated with UV-vis, where it was found that increasing size of R group substituents on the bithiophene linker resulted in a general blue-shift in solution absorbance maximum. The solid-state optical properties of ditopic DAT and B thin films were evaluated by UV-vis, and it was found that the solid-state absorbance was red-shifted with respect to solution absorbance in all cases. The three DAT molecules were vacuum-thermal-deposited onto Au(111) substrates and the morphologies were examined using scanning tunneling microscopy. (DAT-T)2 was observed to organize into six-membered rosettes on the surface, whereas (DAT-TMe)2 formed linear assemblies before and after thermal annealing. For (DAT-Toct)2 , an irregular arrangement was observed, while (B-TMe)2 showed several co-existent assembly patterns. The work presented here provides fundamental molecular–supramolecular relationships useful for semiconductive materials design based on ditopic hydrogen-bonding-capable building blocks.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"390 - 404"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1534-1508","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41953913","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}
Chengpeng Wei, Mingyang Liu, Yifei Han, Hua Zhong, Feng Wang
Abstract Supramolecular chirogenesis represents an effective way to induce chirality at the supramolecular level. For the previous host–guest chirogenic systems, metal–ligand coordination, hydrogen bonding, π–π stacking and hydrophobic interactions have been mainly employed as the non-covalent driving forces. In this study, Pt(II)···Pt(II) metal–metal interactions have been engineered to induce supramolecular chirogenesis, by forming non-covalent clipping structures between chiral platinum receptors and achiral platinum guests together. This results in the emergence of Cotton effects in the metal–metal-to-ligand charge transfer region, ascribed to chirality transfer from trans-1,2-diamide cyclohexane unit on chiral receptors to Pt(II)---Pt(II) non-covalent interacting sites. Supramolecular chirogenesis can be further transferred from organic to aqueous solutions, with higher resistance to concentration and temperature variations in the latter medium. Overall, the current study provides new avenues toward supramolecular chirality systems with tailored properties.
{"title":"Supramolecular Chirogenesis Engineered by Pt(II)···Pt(II) Metal–Metal Interactions","authors":"Chengpeng Wei, Mingyang Liu, Yifei Han, Hua Zhong, Feng Wang","doi":"10.1055/a-1512-5965","DOIUrl":"https://doi.org/10.1055/a-1512-5965","url":null,"abstract":"Abstract Supramolecular chirogenesis represents an effective way to induce chirality at the supramolecular level. For the previous host–guest chirogenic systems, metal–ligand coordination, hydrogen bonding, π–π stacking and hydrophobic interactions have been mainly employed as the non-covalent driving forces. In this study, Pt(II)···Pt(II) metal–metal interactions have been engineered to induce supramolecular chirogenesis, by forming non-covalent clipping structures between chiral platinum receptors and achiral platinum guests together. This results in the emergence of Cotton effects in the metal–metal-to-ligand charge transfer region, ascribed to chirality transfer from trans-1,2-diamide cyclohexane unit on chiral receptors to Pt(II)---Pt(II) non-covalent interacting sites. Supramolecular chirogenesis can be further transferred from organic to aqueous solutions, with higher resistance to concentration and temperature variations in the latter medium. Overall, the current study provides new avenues toward supramolecular chirality systems with tailored properties.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"374 - 380"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1512-5965","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47858289","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}
Lukas Ahrens, Yvonne J. Hofstetter, Barış Çelik, J. Butscher, F. Rominger, Jan Freudenberg, Y. Vaynzof, U. Bunz
Abstract Two covalently linked triisopropylsilyl-ethynylated phenazinothiadiazoles were prepared through condensation of a spirocyclic and a bicyclic tetraketone with a 5,6-diaminobenzothiadiazole. The spirobisindene- and the ethanoanthracene-based linkers render the electron acceptors amorphous in thin films. The optoelectronic properties of the non-conjugated dimers are indistinguishable from that of the crystalline monomer. Bulk heterojunction solar cells were prepared with power conversion efficiencies peaking at 1.6%. The choice of linker neither influenced optical and electrochemical properties nor device performance.
{"title":"Dimeric Phenazinothiadiazole Acceptors in Bulk Heterojunction Solar Cells","authors":"Lukas Ahrens, Yvonne J. Hofstetter, Barış Çelik, J. Butscher, F. Rominger, Jan Freudenberg, Y. Vaynzof, U. Bunz","doi":"10.1055/s-0041-1726459","DOIUrl":"https://doi.org/10.1055/s-0041-1726459","url":null,"abstract":"Abstract Two covalently linked triisopropylsilyl-ethynylated phenazinothiadiazoles were prepared through condensation of a spirocyclic and a bicyclic tetraketone with a 5,6-diaminobenzothiadiazole. The spirobisindene- and the ethanoanthracene-based linkers render the electron acceptors amorphous in thin films. The optoelectronic properties of the non-conjugated dimers are indistinguishable from that of the crystalline monomer. Bulk heterojunction solar cells were prepared with power conversion efficiencies peaking at 1.6%. The choice of linker neither influenced optical and electrochemical properties nor device performance.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"168 - 173"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/s-0041-1726459","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"45247041","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 great potential of subphthalocyanines (SubPcs) to stabilize boron peroxides has been demonstrated. In particular, a subphthalocyanato boron (III) peroxide has been prepared in good yield via boron triflate. This derivative is remarkably stable under ambient conditions and can be fully characterized. The impact of the peroxide group on the structural and optoelectronic properties of SubPc was examined by NMR and UV/Vis spectroscopies, as well as single-crystal X-ray diffraction analysis. Moreover, density functional theory calculations were performed to explain the experimental results. The reactivity of this peculiar boron peroxide as an oxidant and a Lewis base was also studied.
{"title":"Boosting the Stability of Boron Peroxides through Subphthalocyanine Coordination","authors":"Jorge Labella, Elisa López-Serrano, T. Torres","doi":"10.1055/s-0041-1727093","DOIUrl":"https://doi.org/10.1055/s-0041-1727093","url":null,"abstract":"Abstract The great potential of subphthalocyanines (SubPcs) to stabilize boron peroxides has been demonstrated. In particular, a subphthalocyanato boron (III) peroxide has been prepared in good yield via boron triflate. This derivative is remarkably stable under ambient conditions and can be fully characterized. The impact of the peroxide group on the structural and optoelectronic properties of SubPc was examined by NMR and UV/Vis spectroscopies, as well as single-crystal X-ray diffraction analysis. Moreover, density functional theory calculations were performed to explain the experimental results. The reactivity of this peculiar boron peroxide as an oxidant and a Lewis base was also studied.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"141 - 145"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/s-0041-1727093","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"44153943","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 Side-chain engineering is an important strategy in designing novel polymer semiconductor materials for high-efficient organic solar cells. The use of trialkylsilyl side chains can improve the photovoltaic efficiency by decreasing the energy of the HOMO of the polymer and improving its crystallinity and hole mobility. Compared to simple linear derivatives, α-branching in the alkyl groups of trialkylsilyl side chains causes strong aggregation and excessive phase separation in the photoactive layer, leading to poor device performance. β-Branching of the alkyl groups has not yet been used in trialkylsilyl side chains. Herein, we describe a new polymer (J77) with triisobutylsilyl side chains to investigate the effect of β-branching on the molecular aggregation, optical properties, energy levels, and photovoltaic properties. We find that compared to α-branching, β-branching of alkyl groups in trialkylsilyl side chains significantly reduces aggregation. This enables J77 to form blend morphologies in films that provide high-efficient solar cells in combination with different non-fullerene acceptors. Moreover β-branching of the alkyl groups in trialkylsilyl side chains lowers the HOMO energy level of J77 and increases the open-circuit voltage of J77-based solar cells without sacrificing short-circuit current density or fill factor.
{"title":"Efficient Solar Cells Based on a Polymer Donor with β-Branching in Trialkylsilyl Side Chains","authors":"Haijun Bin, M. Wienk, R. Janssen","doi":"10.1055/s-0041-1726427","DOIUrl":"https://doi.org/10.1055/s-0041-1726427","url":null,"abstract":"Abstract Side-chain engineering is an important strategy in designing novel polymer semiconductor materials for high-efficient organic solar cells. The use of trialkylsilyl side chains can improve the photovoltaic efficiency by decreasing the energy of the HOMO of the polymer and improving its crystallinity and hole mobility. Compared to simple linear derivatives, α-branching in the alkyl groups of trialkylsilyl side chains causes strong aggregation and excessive phase separation in the photoactive layer, leading to poor device performance. β-Branching of the alkyl groups has not yet been used in trialkylsilyl side chains. Herein, we describe a new polymer (J77) with triisobutylsilyl side chains to investigate the effect of β-branching on the molecular aggregation, optical properties, energy levels, and photovoltaic properties. We find that compared to α-branching, β-branching of alkyl groups in trialkylsilyl side chains significantly reduces aggregation. This enables J77 to form blend morphologies in films that provide high-efficient solar cells in combination with different non-fullerene acceptors. Moreover β-branching of the alkyl groups in trialkylsilyl side chains lowers the HOMO energy level of J77 and increases the open-circuit voltage of J77-based solar cells without sacrificing short-circuit current density or fill factor.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"134 - 140"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/s-0041-1726427","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"47287420","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}
I. Zharinova, Nicolau Saker Neto, Tze Cin Owyong, J. White, Wallace W. H. Wong
Abstract Oligo(p-phenylene)s with a donor phenol group and an acceptor pyridinium moiety separated by one and two p-phenylene units were synthesized by the linear iterative Suzuki–Miyaura coupling method using aryl nonaflates as effective coupling reagents. Zwitterionic forms of these push–pull molecules were generated upon deprotonation of the phenol leading to large redshifts in absorbance maxima. UV-vis absorbance studies also revealed strong dependence of the band position on solvent polarity: a smooth bathochromic shift can be observed with the decrease of the solvent polarity. The molecule with one p-phenylene bridging unit showed the strongest solvatochromic characteristics in the series, spanning the range of 167 nm while moving from polar water to less polar N,N-dimethylformamide. The magnitude of this shift was close to Reichardt's dye — one of the most solvatochromic organic dyes known.
{"title":"Synthesis and Solvatochromic Behavior of Zwitterionic Donor–Bridge–Acceptor Systems with Oligo(p-phenylene) Spacers","authors":"I. Zharinova, Nicolau Saker Neto, Tze Cin Owyong, J. White, Wallace W. H. Wong","doi":"10.1055/s-0041-1725075","DOIUrl":"https://doi.org/10.1055/s-0041-1725075","url":null,"abstract":"Abstract Oligo(p-phenylene)s with a donor phenol group and an acceptor pyridinium moiety separated by one and two p-phenylene units were synthesized by the linear iterative Suzuki–Miyaura coupling method using aryl nonaflates as effective coupling reagents. Zwitterionic forms of these push–pull molecules were generated upon deprotonation of the phenol leading to large redshifts in absorbance maxima. UV-vis absorbance studies also revealed strong dependence of the band position on solvent polarity: a smooth bathochromic shift can be observed with the decrease of the solvent polarity. The molecule with one p-phenylene bridging unit showed the strongest solvatochromic characteristics in the series, spanning the range of 167 nm while moving from polar water to less polar N,N-dimethylformamide. The magnitude of this shift was close to Reichardt's dye — one of the most solvatochromic organic dyes known.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"103 - 118"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/s-0041-1725075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42192833","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 Supramolecular nanostructured thiophene based materials with optoelectronic functions are of wide current interest and are playing a crucial role in different fields of nanoscience and nanotechnology. This short review gives a concise report of some particularly interesting examples from our own work concerning thiophene-based supramolecular architectures at multiple length scales, their function and application in devices. We start with some general considerations on the great chemical diversity of thiophene derivatives and their supramolecular architectures. Then we focus on how the supramolecular organization of specific thiophene derivatives may generate nanostructures that enable new functions and applications in devices. For each example, we report the synthesis of the corresponding thiophene derivatives. 1. Introduction 2. Supramolecular Organization may Impart New Functions to the System 3. Supramolecular and Optoelectronic Properties of Oligothiophene-S,S-dioxides 4. Colloidal Nanoparticles formed by Self-Assembly of Thiophene-Based Polymers 5. Conclusions and Outlook
{"title":"Supramolecular Thiophene-Based Materials: A Few Examples of the Interplay between Synthesis, Optoelectronic Properties and Applications","authors":"F. Di Maria, M. Zangoli, G. Barbarella","doi":"10.1055/s-0041-1730934","DOIUrl":"https://doi.org/10.1055/s-0041-1730934","url":null,"abstract":"Abstract Supramolecular nanostructured thiophene based materials with optoelectronic functions are of wide current interest and are playing a crucial role in different fields of nanoscience and nanotechnology. This short review gives a concise report of some particularly interesting examples from our own work concerning thiophene-based supramolecular architectures at multiple length scales, their function and application in devices. We start with some general considerations on the great chemical diversity of thiophene derivatives and their supramolecular architectures. Then we focus on how the supramolecular organization of specific thiophene derivatives may generate nanostructures that enable new functions and applications in devices. For each example, we report the synthesis of the corresponding thiophene derivatives. 1. Introduction 2. Supramolecular Organization may Impart New Functions to the System 3. Supramolecular and Optoelectronic Properties of Oligothiophene-S,S-dioxides 4. Colloidal Nanoparticles formed by Self-Assembly of Thiophene-Based Polymers 5. Conclusions and Outlook","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"321 - 336"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/s-0041-1730934","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"42218481","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 Dithienothiazine copolymers are efficiently obtained by Suzuki polymerization or in situ lithiation–Negishi polymerization in good to excellent yields. Gel permeation chromatography was applied to characterize the dispersities and degrees of polymerization of these novel materials. Thermogravimetric analysis shows that the copolymers are stable towards side-chain cleavage up to 200 °C. The materials are deep red to black amorphous solids or resins and their absorption and emission spectra in solution reveal broad absorption bands in the visible and orange to deep red luminescence upon UV excitation. According to the optical band gaps these novel copolymers qualify as a new class of low band gap organic semiconductors.
{"title":"Dithienothiazine Copolymers – Synthesis and Electronic Properties of Novel Redox-Active Fluorescent Polymers","authors":"J. Nau, T. Mueller","doi":"10.1055/a-1528-6301","DOIUrl":"https://doi.org/10.1055/a-1528-6301","url":null,"abstract":"Abstract Dithienothiazine copolymers are efficiently obtained by Suzuki polymerization or in situ lithiation–Negishi polymerization in good to excellent yields. Gel permeation chromatography was applied to characterize the dispersities and degrees of polymerization of these novel materials. Thermogravimetric analysis shows that the copolymers are stable towards side-chain cleavage up to 200 °C. The materials are deep red to black amorphous solids or resins and their absorption and emission spectra in solution reveal broad absorption bands in the visible and orange to deep red luminescence upon UV excitation. According to the optical band gaps these novel copolymers qualify as a new class of low band gap organic semiconductors.","PeriodicalId":93348,"journal":{"name":"Organic Materials","volume":"03 1","pages":"381 - 389"},"PeriodicalIF":0.0,"publicationDate":"2021-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1055/a-1528-6301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49180195","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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