Design and synthesis of organic materials for energy storage, optoelectronic applications and as templates for novel types of nanotubes
Final Report Abstract
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)
Publications
- “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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at 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
(See online at https://doi.org/10.1021/acs.joc.9b01195)
