Publications
39 results found
Eder S, Yoo DJ, Nogala W, et al., 2020, Switching between Local and Global Aromaticity in a Conjugated Macrocycle for High-Performance Organic Sodium-Ion Battery Anodes, Angewandte Chemie, Vol: 132, Pages: 13058-13064, ISSN: 0044-8249
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. Aromatic organic compounds can be used as electrode materials in rechargeable batteries and are expected to advance the development of both anode and cathode materials for sodium-ion batteries (SIBs). However, most aromatic organic compounds assessed as anode materials in SIBs to date exhibit significant degradation issues under fast-charge/discharge conditions and unsatisfying long-term cycling performance. Now, a molecular design concept is presented for improving the stability of organic compounds for battery electrodes. The molecular design of the investigated compound, [2.2.2.2]paracyclophane-1,9,17,25-tetraene (PCT), can stabilize the neutral state by local aromaticity and the doubly reduced state by global aromaticity, resulting in an anode material with extraordinarily stable cycling performance and outstanding performance under fast-charge/discharge conditions, demonstrating an exciting new path for the development of electrode materials for SIBs and other types of batteries.
Taublaender MJ, Mezzavilla S, Thiele S, et al., 2020, Hydrothermal Generation of Conjugated Polymers Using the Example of Pyrrone Polymers and Polybenzimidazoles, Angewandte Chemie, ISSN: 0044-8249
Taublaender MJ, Mezzavilla S, Thiele S, et al., 2020, Hydrothermal Generation of Conjugated Polymers Using the Example of Pyrrone Polymers and Polybenzimidazoles, Angewandte Chemie International Edition, ISSN: 1433-7851
Eder S, Yoo D-J, Nogala W, et al., 2020, Switching between local and global aromaticity in a conjugated macrocycle for high-performance organic sodium-ion battery anodes, Angewandte Chemie International Edition, Vol: 59, Pages: 12958-12964, ISSN: 1433-7851
Aromatic organic compounds can be used as electrode materials in rechargeable batteries and are expected to advance the development of both anode and cathode materials for sodium-ion batteries (SIBs). However, most aromatic organic compounds assessed as anode materials in SIBs to date exhibit significant degradation issues under fast-charge/discharge conditions and unsatisfying long-term cycling performance. Now, a molecular design concept is presented for improving the stability of organic compounds for battery electrodes. The molecular design of the investigated compound, [2.2.2.2]paracyclophane-1,9,17,25-tetraene (PCT), can stabilize the neutral state by local aromaticity and the doubly reduced state by global aromaticity, resulting in an anode material with extraordinarily stable cycling performance and outstanding performance under fast-charge/discharge conditions, demonstrating an exciting new path for the development of electrode materials for SIBs and other types of batteries.
Meindl B, Pfennigbauer K, Stöger B, et al., 2020, Double ring-closing approach for the synthesis of 2,3,6,7-substituted anthracene derivatives., Journal of Organic Chemistry, Vol: 85, Pages: 8240-8244, ISSN: 0022-3263
A method for the synthesis of 2,3,6,7-substituted anthracene derivatives, one of the most challenging anthracene substitution patterns to obtain, is presented. The method is exemplified by the preparation of 2,3,6,7-anthracenetetracarbonitrile and employs a newly developed, stable, protected 1,2,4,5-benzenetetracarbaldehyde as the precursor. The precursor can be obtained in two scalable synthetic steps from 2,5-dibromoterephthalaldehyde and is converted into the anthracene derivative by a double intermolecular Wittig reaction under very mild conditions, followed by a deprotection and intramolecular double ring-closing condensation reaction.
Taublaender MJ, Mezzavilla S, Thiele S, et al., 2020, Hydrothermale Synthese von konjugierten Polymeren am Beispiel von Pyrronpolymeren und Polybenzimidazolen, Angewandte Chemie, ISSN: 0044-8249
Hodsden T, Thorley KJ, Panidi J, et al., 2020, Core fluorination enhances solubility and ambient stability of an IDT‐based n‐type semiconductor in transistor devices, Advanced Functional Materials, Vol: 30, Pages: 1-12, ISSN: 1616-301X
The synthesis of a novel fluorinated n‐type small molecule based on an indacenodithiophene core is reported. Fluorination is found to have a significant impact on the physical properties, including a surprisingly dramatic improvement in solubility, in addition to effectively stabilizing the lowest‐unoccupied molecular orbital energy (−4.24 eV). Single‐crystal analysis and density functional theory calculations indicate the improved solubility can be attributed to backbone torsion resulting from the positioning of the fluorine group in close proximity to the strongly electron‐withdrawing dicyanomethylene group. Organic thin‐film transistors made via blade coating display high electron mobility (up to 0.49 cm2 V−1 s−1) along with good retention of performance in ambient conditions.
Taublaender MJ, Mezzavilla S, Thiele S, et al., 2020, Hydrothermal generation of conjugated polymers using the example of pyrrone polymers and polybenzimidazoles., Angewandte Chemie International Edition, ISSN: 1433-7851
Various polyimides and polyamides have recently been prepared via hydrothermal synthesis in nothing but H2 O under high-pressure and high-temperature conditions. However, none of the prepared polymers feature a truly conjugated polymer backbone. Here, we report on an expansion of the synthetic scope of this straightforward and inherently environmentally friendly polymerization technique to the generation of conjugated polymers. Selected representatives of two different polymer classes, pyrrone polymers and polybenzimidazoles, were generated hydrothermally. We present a mechanistic discussion of the polymer formation process as well as an electrochemical characterization of the most promising product.
Rosspeintner A, Glöcklhofer F, Pasitsuparoad P, et al., 2019, Effect of symmetric and asymmetric substitution on the optoelectronic properties of 9,10-dicyanoanthracene†, Molecular Systems Design and Engineering, Vol: 4, Pages: 951-961, ISSN: 2058-9689
A set of substituted 9,10-dicyanoanthracenes (DCA) has been synthesized, their photophysical and electrochemical properties in liquid solution have been characterized and supplemented by high level ab initio quantum chemical calculations. Three different methoxy-group-containing substituents have been linked to the DCA core in a symmetric and asymmetric fashion to produce six different species with strong quadrupole and dipole moments, respectively. The major difference between the symmetrically and asymmetrically substituted species are the enhanced two-photon absorption intensities of the former. In most of the cases studied, the molecules show reasonably large optical transition probabilities. The fluorescence brightness of these substances makes them interesting objects for two-photon absorption applications. Additionally, all molecules can be both easily reduced and oxidized electrochemically and are therefore suitable for optoelectronic applications. </p> </div> </div> </div>
Reichsöllner E, Creamer A, Cong S, et al., 2019, Fast and selective post-polymerization modification of conjugated polymers using dimethyldioxirane, Frontiers in Chemistry, Vol: 7, ISSN: 2296-2646
Modification of functional groups attached to conjugated polymer backbones can drastically alter the material properties. Oxidation of electron-donating thioalkyl substituents to electron-withdrawing sulfoxides or sulfones is a particularly effective modification. However, so far, this reaction has not been studied for the modification of conjugated polymers used in organic electronics. Crucial questions regarding selectivity and reaction time waited to be addressed. Here, we show that the reaction is highly selective and complete within just a few minutes when using dimethyldioxirane (DMDO) for the oxidation of thioalkyl substituents attached to the well-investigated conjugated polymers poly(9-(1-octylnonyl)carbazole-alt-4,7-dithienylbenzothiadiazole) (PCDTBT) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT). The selectivity was confirmed by comparison with polymers obtained from pre-oxidized monomers and by control experiments using related polymers without thioalkyl substituents. Using DMDO, the oxidation yields acetone as the only side-product, which reduces the work-up to mere evaporation of solvents and excessive reagent. Our results show that this oxidation is an exciting method for the preparation of electron-deficient conjugated polymers. It may even allow the preparation of electron acceptors for solar cells directly from the electron donors.
Rimmele M, Ableidinger K, Marsh AV, et al., 2019, Thioalkyl- and Sulfone-Substituted Poly(p-Phenylene Vinylene)s, Polymer Chemistry, Vol: 10, Pages: 738-750, ISSN: 1759-9954
Poly(p-phenylene vinylene)s (PPVs) have been studied for decades, but research on this interesting class of conjugated polymers is far from being completed. New applications like in bioimaging keep emerging and even simple structural variations are still waiting to be explored. Surprisingly, not even dithioalkyl-substituted PPVs (S-PPVs) have been reported in the peer-reviewed literature, although the corresponding dialkoxy-substituted PPVs (O-PPVs) like MEH-PPV or MDMO-PPV are most frequently used and although thioalkyl substituents can improve the material properties significantly. We herein report the development of a highly efficient, scalable two-step synthesis of Gilch monomers for S-PPVs starting from low-cost 1,4-diiodobenzene. A low-temperature polymerization protocol has been developed for these monomers, affording high-molecular weight S-PPVs in excellent yields. The thermal, electrochemical, and photophysical properties of S-PPVs are reported to highlight the potential of these polymers. Furthermore, treatment with dimethyldioxirane is demonstrated to result in rapid conversion into sulfone-substituted PPVs (SO2-PPVs), introducing a route to high-molecular weight SO2-PPVs with exceptional stability and solid-state photoluminescence quantum yields of up to 0.46.
Reichsöllner E, Creamer A, Cong S, et al., 2019, Fast and selective post-polymerization modification of conjugated polymers using dimethyldioxirane.
Modification of functional groups attached to conjugated polymer backbones can drastically alter the material properties. Oxidation of electron-donating thioalkyl substituents to electron-withdrawing sulfoxides or sulfones is a particularly effective modification. However, so far, this reaction has not been studied for the modification of conjugated polymers used in organic electronics. Crucial questions regarding selectivity and reaction time waited to be addressed. Here, we show that the reaction is highly selective and complete within just a few minutes when using dimethyldioxirane (DMDO) for the oxidation of thioalkyl substituents attached to the well investigated conjugated polymers poly(9-(1-octylnonyl)carbazole-alt-4,7-dithienylbenzothiadiazole) (PCDTBT) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT). The selectivity was confirmed by comparison with polymers obtained from pre-oxidized monomers and by control experiments using related polymers without thioalkyl substituents. Using DMDO, the oxidation yields acetone as the only side-product, which reduces the work-up to mere evaporation of solvents and excessive reagent. Our results show that this oxidation is an exciting method for the preparation of electron-deficient conjugated polymers. It may even allow the preparation of electron acceptors for solar cells directly from the electron donors.
Glöcklhofer F, Rosspeintner A, Pasitsuparoad P, et al., 2019, Effect of symmetric and asymmetric substitution on the optoelectronic properties of 9,10-dicyanoanthracene, Molecular Systems Design & Engineering, Vol: 4, Pages: 951-961
<p>Six newly synthesised 9,10-dicyanoanthracene derivatives exhibit high two-photon absorption cross sections particularly upon symmetric substitution with strong electron donors.</p>
Rimmele M, Ableidinger K, Marsh A, et al., 2018, Thioalkyl- and Sulfone-Substituted Poly(p-Phenylene Vinylene)s, Publisher: Royal society of chemistry
Poly(p-phenylene vinylene)s (PPVs) have been studied for decades, but research on this interesting class of conjugated polymers is far from being completed. New applications like in bioimaging keep emerging and even simple structural variations are still waiting to be explored. Surprisingly, not even dithioalkyl-substituted PPVs (S-PPVs) have been reported in the peer-reviewed literature, although the corresponding dialkoxy-substituted PPVs (O-PPVs) like MEH-PPV or MDMO-PPV are most frequently used and although thioalkyl substituents can improve the material properties significantly. We herein report the development of a highly efficient, scalable two-step synthesis of Gilch monomers for S-PPVs starting from low-cost 1,4-diiodobenzene. A low-temperature polymerization protocol has been developed for these monomers, affording high-molecular weight S-PPVs in excellent yields. The thermal, electrochemical, and photophysical properties of S-PPVs are reported to highlight the potential of these polymers. Furthermore, treatment with dimethyldioxirane is demonstrated to result in rapid conversion into sulfone-substituted PPVs (SO<sub>2</sub>-PPVs), introducing a route to high-molecular weight SO<sub>2</sub>-PPVs with exceptional stability and solid-state photoluminescence quantum yields of up to 0.46.
Taublaender MJ, Glöcklhofer F, Marchetti-Deschmann M, et al., 2018, Inside Cover: Green and Rapid Hydrothermal Crystallization and Synthesis of Fully Conjugated Aromatic Compounds (Angew. Chem. Int. Ed. 38/2018), Angewandte Chemie International Edition, Vol: 57, Pages: 12180-12180, ISSN: 1433-7851
Taublaender MJ, Glöcklhofer F, Marchetti-Deschmann M, et al., 2018, Innentitelbild: Grüne und rasche hydrothermale Kristallisation und Synthese vollständig konjugierter aromatischer Verbindungen (Angew. Chem. 38/2018), Angewandte Chemie, Vol: 130, Pages: 12358-12358, ISSN: 0044-8249
Taublaender MJ, Glöcklhofer F, Marchetti-Deschmann M, et al., 2018, Green and Rapid Hydrothermal Crystallization and Synthesis of Fully Conjugated Aromatic Compounds, Angewandte Chemie International Edition, Vol: 57, Pages: 12270-12274, ISSN: 1433-7851
Taublaender MJ, Glöcklhofer F, Marchetti-Deschmann M, et al., 2018, Grüne und rasche hydrothermale Kristallisation und Synthese vollständig konjugierter aromatischer Verbindungen, Angewandte Chemie, Vol: 130, Pages: 12450-12454, ISSN: 0044-8249
Gloecklhofer F, Stoeger B, Froehlich J, 2018, Synthesis of 1,2,5,6-and 1,4,5,8-anthracenetetrone: Building blocks for -conjugated small molecules and polymers, SYNTHETIC COMMUNICATIONS, Vol: 48, Pages: 2358-2365, ISSN: 0039-7911
Glöcklhofer F, Stöger B, Fröhlich J, 2018, Synthesis of 1,2,5,6- and 1,4,5,8-anthracenetetrone: Building blocks for π-conjugated small molecules and polymers, Synthetic Communications, Vol: 48, Pages: 2358-2365, ISSN: 0039-7911
Reliable reactions for the synthesis of two interesting anthracenetetrones have been identified and optimized. Both syntheses start from dihydroxy-9,10-anthraquinones and were selected for maximized efficiency and minimized work load. Work-up of all reactions can be achieved without column chromatography, which facilitates further scale-up. So far, both target compounds are considerably underexplored despite their promising molecular structure for use in devices and in organic synthesis, especially as building blocks for π-conjugated compounds. The crystal structure of 1,4,5,8-anthracentetrone is reported.
Kautny P, Glöcklhofer F, Kader T, et al., 2017, Charge-transfer states in triazole linked donor–acceptor materials: strong effects of chemical modification and solvation, Physical Chemistry Chemical Physics, Vol: 19, Pages: 18055-18067, ISSN: 1463-9076
<p>A new series of push–pull chromophores are synthesized, spectroscopically characterized, and their excited state energies and wavefunctions are elucidated by high-level computational methods.</p>
Gloecklhofer F, Morawietz AJ, Stoeger B, et al., 2017, Extending the scope of a new cyanation: design and synthesis of an anthracene derivative with an exceptionally low LUMO level and improved solubility, ACS Omega, Vol: 2, Pages: 1594-1600, ISSN: 2470-1343
The preparation of cyanated acenes from quinones has been improved for the conversion of electron-poor starting materials. The new procedure was used to prepare rationally designed 2,7-dinitro-9,10-dicyanoanthracene. Crystallographic, morphological, and electrochemical investigations have revealed most promising properties for applications in organic electronics.
Gloecklhofer F, Kautny P, Fritz P, et al., 2017, Using Dicyanoanthracene Triflates as Superior Precursors: Modifying Properties by Sterically Hindered Aryl Substituents, CHEMPHOTOCHEM, Vol: 1, Pages: 51-55, ISSN: 2367-0932
Lumpi D, Steindl J, Steiner S, et al., 2017, Thiophene ring-fragmentation reactions: Principles and scale-up towards NLO materials, TETRAHEDRON, Vol: 73, Pages: 472-480, ISSN: 0040-4020
Glöcklhofer F, Kautny P, Fritz P, et al., 2017, Back Cover: Using Dicyanoanthracene Triflates as Superior Precursors: Modifying Properties by Sterically Hindered Aryl Substituents (ChemPhotoChem 2/2017), ChemPhotoChem, Vol: 1, Pages: 76-76, ISSN: 2367-0932
Glöcklhofer F, Petritz A, Karner E, et al., 2017, Dicyano- and tetracyanopentacene: foundation of an intriguing new class of easy-to-synthesize organic semiconductors, Journal of Materials Chemistry C, Vol: 5, Pages: 2603-2610, ISSN: 2050-7526
<p>Extraordinarily low LUMO levels, dense molecular packing, an intriguing packing motif, reversible bleaching and OTFT operability under ambient conditions are revealed in a detailed investigation of multi-cyanated pentacenes.</p>
Glöcklhofer F, Lunzer M, Stöger B, et al., 2016, Cover Picture: A Versatile One-Pot Access to Cyanoarenes from ortho- and para-Quinones: Paving the Way for Cyanated Functional Materials (Chem. Eur. J. 15/2016), Chemistry - A European Journal, Vol: 22, Pages: 5021-5021, ISSN: 0947-6539
Glöcklhofer F, Lunzer M, Stöger B, et al., 2016, A Versatile One-Pot Access to Cyanoarenes from ortho- and para-Quinones: Paving the Way for Cyanated Functional Materials, Chemistry - A European Journal, Vol: 22, Pages: 5025-5025, ISSN: 0947-6539
Glöcklhofer F, Lunzer M, Stöger B, et al., 2016, A Versatile One-Pot Access to Cyanoarenes from ortho- and para-Quinones: Paving the Way for Cyanated Functional Materials, Chemistry - A European Journal, Vol: 22, Pages: 5173-5180, ISSN: 0947-6539
Sohr B, Glöcklhofer F, Stöger B, et al., 2016, cis,trans,cis-1,2,3,4-Tetrakis[2-(ethylsulfanyl)phenyl]cyclobutane, IUCrData, Vol: 1
<jats:p>The title cyclobutane derivative, C<jats:sub>36</jats:sub>H<jats:sub>40</jats:sub>S<jats:sub>4</jats:sub>, formed serendipitously through a photochemically initiated [2 + 2] cycloaddition. The asymmetric unit contains half a molecule with the 2-(ethylsulfanyl)phenyl substituents in a<jats:italic>cis</jats:italic>configuration, the other half of the molecule being generated by the application of a twofold rotation operation. The substituents in both halves of the molecules are in a<jats:italic>trans</jats:italic>arrangement relative to each other. The cyclobutane ring shows angular and torsional strains, with C—C—C bond angles of 89.80 (8) and 88.40 (8)°, and an average absolute torsion angle of 14.28 (10)°. The angle of pucker in the ring is 20.27 (12)°. The C<jats:sub>cb</jats:sub>—C<jats:sub>cb</jats:sub>—C<jats:sub>b</jats:sub>angles between the cyclobutane (cb) ring atoms and the attached benzene (b) ring atoms are widened and range from 115.19 (10) to 121.66 (10)°. A weak intramolecular C—H...S hydrogen-bonding interaction between one of the cyclobutane ring H atoms and the S atom may help to establish the molecular conformation. No specific intermolecular interactions are found.</jats:p>
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