Entwicklung organischer Materialien zur Energiespeicherung, für elektrooptische Anwendungen und als Template für neuartige Nanoröhren
Zusammenfassung der Projektergebnisse
In the field of organic battery materials, we developed a variety of redox-active polymers and assessed their suitability as electrode materials for batteries. This includes phenothiazine, thianthrene, cyclooctatetraene and azines as redox-active groups in side-group functionalized polymers or polymers containing the redox-active groups in the main chain. Outstanding results were obtained for phenothiazine-based polymers, which showed ultra-high cycling stabilities and rate capabilities up to 100C in lithium-organic battery cells. A record in cell potential of 4.1 V was demonstrated with a thianthrene-based polymer. Incorporating spiro-conjugated units into donor-acceptor-type materials provided dyes with tunable optical properties and charge-transfer transitions. A range of dyes with both donor−σ−acceptor design, in which donor and acceptor are connected through a spiro-center, as well as donor-acceptor structure with tetraaminospirenes as donors were synthesized. While the spiro-connected donor−σ−acceptor dyes were non-emissive, the latter showed high photoluminescence quantum yields in solution and tunable emission colors, which makes them attractive as fluorescent emitters. In the area of bent π-systems we reported the first examples of bent antiaromatics using dibenzo[a,e]pentalene (DBP). The DBP unit was bent by incorporation into cyclophane structures. Furthermore, we synthesized the first conjugated nanohoops containing antiaromatic units, namely DBP, as a [2]DBP[12]cycloparaphenylene derivatives. In preparation for these studies we developed versatile synthetic strategies to donor- or acceptor-functionalized DBP derivatives that allowed tuning of their HOMO and LUMO energies. Low-lying LUMO energies and close molecular packing in the solid state resulted in promising n-type conduction in field-effect transistors for thioether-DBPs. Using electron-rich trinuclear gold complexes as donors in supramolecular donor/acceptor interactions, we demonstrated record binding constants to electron-poor π-systems. Such interactions are relevant to the design of chemical sensors. Furthermore, we introduced calix[n]phenothiazines as novel macrocycles with interesting optoelectronic and host properties. Our research on organic battery materials has led to several public media appearances, among others the following: • 2019 YouTube-Video „Organische Batterien“ (https://www.youtube.com/watch?reload=9&v=ZfDKb3yeM9A) • 2018/2019 arte „Xenius: Batterien, Akkus & Co: Neues vom Energiespeicher“ (30.04.2018 and 26.08.2019) • 2018 Gameshow SWR „Sag die Wahrheit“ (26.02.2018, https://www.swr.de/sag-diewahrheit/sendung-vom-26-der-laufententrainer-die-handschuhmacherin-und-mein-bestesstueck/-/id=233244/did=20974676/nid=233244/r9i78w/index.html) • 2017 SWR2 Impuls (Wissen): „Turbo-Akkus ohne Schwermetall“ (08.08.2017, https://www.swr.de/swr2/wissen/article-swr-18064.html)
Projektbezogene Publikationen (Auswahl)
- “Thianthrene-functionalized polynorbornenes as high-voltage materials for organic cathodebased dual-ion batteries“, Chem. Commun. 2015, 51, 15261–15264
M. E. Speer, M. Kolek, J. J. Jassoy, J. Heine, M. Winter, P. M. Bieker, B. Esser
(Siehe online unter https://doi.org/10.1039/c5cc04932f) - “Donor- and acceptor-functionalized dibenzo[a,e]pentalenes: Modulation of the electronic band gap“, Org. Chem. Front. 2017, 4, 658–663
J. Wilbuer, D. C. Grenz, G. Schnakenburg, B. Esser
(Siehe online unter https://doi.org/10.1039/c6qo00487c) - “Ultra-high cycling stability of poly(vinylphenothiazine) as battery cathode material resulting from π-π interactions,“, Energy Environ. Sci. 2017, 10, 2334–2341
M. Kolek, F. Otteny, P. Schmidt, C. Mück-Lichtenfeld, C. Einholz, J. Becking, E. Schleicher, M. Winter, P. M. Bieker, B. Esser
(Siehe online unter https://doi.org/10.1039/c7ee01473b) - “Dibenzo[a,e]pentalenes with Low-Lying LUMO Energy Levels as Potential n-Type Materials,“, J. Org. Chem. 2018, 83, 656– 663
D. C. Grenz, M. Schmidt, D. Kratzert, B. Esser
(Siehe online unter https://doi.org/10.1021/acs.joc.7b02250) - “Dibenzo[a,e]pentalenophanes – Bending a Non-Alternant Hydrocarbon,“, Chem. Eur. J. 2018, 24, 7374–7387
M. Hermann, D. Wassy, D. Kratzert, B. Esser
(Siehe online unter https://doi.org/10.1002/chem.201800322) - “Donor-acceptor interactions between cyclic trinuclear pyridinate gold(I)-complexes and electron-poor guests: Nature and energetics of guest-binding and templating on graphite,“, Chem. Sci. 2018, 9, 3477–3483
R. Hahn, F. Bohle, S. Kotte, T. J. Keller, S.-S. Jester, A. Hansen, S. Grimme, B. Esser
(Siehe online unter https://doi.org/10.1039/c7sc05355j) - “Mechanism of Charge/Discharge of Poly(vinylphenothiazine)-Based Li-Organic Batteries,“, Chem. Mater. 2018, 6, 5420–5426
M. Kolek, F. Otteny, J. Becking, M. Winter, B. Esser, P. Bieker
(Siehe online unter https://doi.org/10.1021/acs.chemmater.8b02015) - “Raising the Bar in Aromatic Donor-Acceptor Interactions with Cyclic Trinuclear Gold(I) Complexes as Strong π-Donors,”, J. Am. Chem. Soc. 2018, 140, 17932–17944
R. Hahn, F. Bohle, W. Fang, A. Walther, S. Grimme, B. Esser
(Siehe online unter https://doi.org/10.1021/jacs.8b08823) - “Thioether- and sulfone-functionalized dibenzopentalenes as n-channel semiconductors for organic field-effect transistors,“, J. Mater. Chem. C 2018, 6, 5420–5426
M. Hermann, R. Wu, D. C. Grenz, D. Kratzert, H. Li, B. Esser
(Siehe online unter https://doi.org/10.1039/c8tc00970h) - “Unlocking Full Discharge Capacities of Poly(vinylphenothiazine) as Battery Cathode Material by Decreasing Polymer Mobility Through Cross-Linking,“, Adv. Energy Mater. 2018, 8, 1802151.
F. Otteny, M. Kolek, J.Becking, M. Winter, P. Bieker, B. Esser
(Siehe online unter https://doi.org/10.1002/aenm.201802151) - “Tuning the optical properties of spiro-centered charge-transfer dyes by extending the donor or acceptor part,”, Org. Chem. Front. 2019, 6, 3649–3656
J. S. Wössner D. C. Grenz, D. Kratzert, B. Esser
(Siehe online unter https://doi.org/10.1039/c9qo01134j) - “π-Conjugation Enables Ultra-High Rate Capabilities and Cycling Stabilities in Phenothiazine Co-Polymers as Cathode-Active Battery Materials,”, Adv. Funct. Mater. 2019, 29, 1906436
P. Acker, L. Rzesny, C. F. N. Marchiori, C. M. Araujo, B. Esser
(Siehe online unter https://doi.org/10.1002/adfm.201906436) - “Azine-based polymers with a two-electron redox process as cathode materials for organic batteries,”, J. Mater. Chem. A 2020, 8, 11195–11201
P. Acker, M. E. Speer, J. S. Wössner, B. Esser
(Siehe online unter https://doi.org/10.1039/d0ta04083e) - “Synthesis and Properties of Conjugated Nanohoops Incorporating Dibenzo[a,e]pentalenes: [2]DBP[12]CPPs,”, J. Org. Chem. 2020, 85, 34–43
D. Wassy, M. Pfeifer, B. Esser
(Siehe online unter https://doi.org/10.1021/acs.joc.9b01195)
