Oliver Dumele

Postdoctoral Fellow


Location: HCI G-320
Phone: +41-44-63-34167
Email:
Oliver Dumele

Education

2006–2011: Diploma studies in Chemistry at Johannes Gutenberg University, Mainz, Germany (Studienstiftung fellowship).
2009: Research stay at UC Berkeley with Prof. J. M. J. Fréchet.
2010–2011: Diploma Thesis at the Max Planck Institute for Polymer Research, Mainz with Prof. K. Müllen.
03/2011–06/2011: Internship at BASF SE, Ludwigshafen.
06/2011–09/2015: Visiting researcher at the National University of Singapore with Prof. Tan Choon-Hong, financed by the Studienstiftung.
11/2011–10/2015: PhD in Supramolecular Organic Chemistry with Prof. F. Diederich at ETH Zürich (funded by a Kekulé scholarship and Studienstiftung des Deutschen Volkes).
11/2015–07/2016: Postdoctoral fellow with Prof. F. Diederich at ETH Zürich.
Since 08/2016: Postdoctoral fellow with Prof. Samuel I. Stupp at Northwestern University, Evanston and Chicago, IL, USA.

Capsules, Cavitands & Complexes – Molecular Recognition based on Halogen Bonding (XB)

Non-covalent interactions are fundamental to understand phenomena related to chemical reactivity, catalysis, drug design, and crystal engineering. We developed a project to investigate the nature of halogen bonding (XB) in solution phase. Halogen bonding describes the supramolecular interaction between the electrophilic site of a bound halogen atom with a Lewis base.

Halogen Bonding

The halogen bonding properties of a library of para-functionalized iodoethynyls was investigated by NMR binding titrations. Van't Hoff analysis revealed the thermodynamic profile (ΔH, ΔS) of the XB interaction and suggested a favorable enthalpy, which can be tuned by remote substituent variations, and an unfavorable entropy term, being constant for all investigated binding partners. These findings were further supported by single crystal X-ray structures of a collection of iodoethynyl benzene derivatives.

Halogen Bonding Capsules

The first example of a well-defined four-point XB supramolecular system was realized by the assembly of two resorcin[4]arene cavitands. NMR binding titrations for F, Cl, Br, and I cavitands as the XB donor show association constants Ka up to 5370 M–1 (ΔG283 K = –4.85 kcal mol–1, for I) even in XB-competitive solvent, where comparable monodentate model systems show no association. The guest-binding capabilities inside the dimeric capsules were studied: guest molecules (1,4-dioxane or 1,4-dithiane) are encapsulated in two separate cavities within the XB capsule, with high affinities up to Ka = 9.0✕108 M–2 (ΔG283 K = –11.6 kcal mol–1).


Publications

  1. T. D. Schladt, K. Koll, S. Prüfer, H. Bauer, F. Natalio, O. Dumele, R. Raidoo, S. Weber, U. Wolfrum, L. M. Schreiber, M. P. Radsak, H. Schild, W. Tremel, J. Mater. Chem. 2012, 22, 9253–9262. Multifunctional Superparamagnetic MnO@SiO2 Core/Shell Nanoparticles and their Application for Optical and Magnetic Resonance Imaging.
  2. A. D. Finke, O. Dumele, M. Zalibera, D. Confortin, P. Cias, G. Jayamurugan, J.-P. Gisselbrecht, C. Boudon, W. B. Schweizer, G. Gescheidt, F. Diederich, J. Am. Chem. Soc. 2012, 134, 18139–18146. 6,6-Dicyanopentafulvenes: Electronic Structure and Regioselectivity in [2+2] Cycloaddition–Retroelectrocyclization Reactions.
  3. T. Wang, A. Pfisterer, S. L. Kuan, Y. Wu, O. Dumele, M. Lamia, K. Müllen, T. Weil, Chem. Sci. 2013, 4, 1889–1894. Cross-conjugation of DNA, Proteins and Peptides via a pH Switch.
  4. G. Jayamurugan, O. Dumele, J.-P. Gisselbrecht, C. Boudon, W. B. Schweizer, B. Bernet, F. Diederich, J. Am. Chem. Soc. 2013, 135, 2599–3606. Expanding the Chemical Structure Space of Opto-Electronic Molecular Materials: Unprecedented Push–Pull Chromophores by Reaction of a Donor-Substituted Tetracyanofulvene with Electron-Rich Alkynes
  5. J. Roose, S. Achermann, O. Dumele, F. Diederich, Eur. J. Org. Chem. 2013, 3223–3231. Electronically Connected [n]Helicenes: Synthesis and Chiroptical Properties of Enantiomerically Pure (E)-1,2-Di([6]helicen-2-yl)ethenes. Cover Page of Eur. J. Org. Chem. 16/2013.
  6. M. Štefko, M. D. Tzirakis, B. Breiten, M.-O. Ebert, O. Dumele, W. B. Schweizer, J.-P. Gisselbrecht, C. Boudon, M. T. R. Beels, I. Biaggio, F. Diederich, Chem. Eur. J. 2013, 19, 12693–12704. Donor–Acceptor (D–A)-substituted Polyyne Chromophores: Modulation of Their Optoelectronic Properties by Varying the Length of the Acetylene Spacer.
  7. C. Dengiz, O. Dumele, S.-i. Kato, M. Zalibera, P. Cias, W. B. Schweizer, C. Boudon, J.-P. Gisselbrecht, G. Gescheidt, F. Diederich, Chem. Eur. J. 2014, 20, 1279–1286. From Homoconjugated Push–Pull Chromophores to Donor–Acceptor-Substituted Spiro-Systems by Thermal Rearrangement.
  8. G. London, M. v. W. Rekowski, O. Dumele, W. B. Schweizer, J.-P. Gisselbrecht, C. Boudon, F. Diederich, Chem. Sci. 2014, 5, 965–972. Pentalenes with Novel Topologies: Exploiting the Cascade Carbopalladation Reaction between Alkynes and gem-Dibromoolefins.
  9. O. Dumele, D. Wu, N. Trapp, N. Goroff, F. Diederich, Org. Lett. 2014, 18, 4722–4725. Halogen Bonding of (Iodoethynyl)benzene Derivatives in Solution. Highlighted in ACS Editor’s Choice.
  10. T. Wang, Y. Wu, S. L. Kuan, O. Dumele, D. Y. W. Ng, M. Arzt, J. Thomas, M. Lamla, C. Barner-Kowollik, T. Weil, Chem. Eur. J. 2014, 21, 228–238. A Disulfide Intercalator Toolbox for Site-Directed Protein Chemistry. Highlighted as Hot Paper.
  11. J. Cao, G. London, O. Dumele, M. v. W. Rekowski, N. Trapp, L. Ruhlmann, C. Boudon, A. Stanger, F. Diederich, J. Am. Chem. Soc. 2015, 137, 7178–7188.  The Impact of Antiaromatic Subunits in [4n+2] p Systems: Bispentalenes with [4n+2]-Electron Perimeter but Antiaromatic Character. —Highlighted in Synfacts 2015, 11, 0814 and in Chimia 2015, 69, 549.
  12. E. Persch,† O. Dumele,† F. Diederich, Angew. Chem. Int. Ed. 2015, 54, 3290–3327. Molecular Recognition in Chemical and Biological Systems.
  13. O. Dumele, N. Trapp, F. Diederich, Angew. Chem. Int. Ed. 2015, 54, 12339–12344. Halogen Bonding Molecular Capsules. —Highlighted in Synfacts 2015, 11, 0813.
  14. B. S. Lauber, A. K. Asraful, L. A. Hardegger, L. B. Aarmo, O. Dumele, M. Harder, B. Kuhn, R. A. Engh, F. Diederich, Chem. Eur. J. 2016, 22, 211–221. Addressing the Glycine-Rich Loop of Protein Kinases by a Multi-Facetted Interaction Network: Inhibition of PKA and a PKB Mimic.
  15. C. Hohn, A. Härtsch, T. Pfaffeneder, F. Ehrmann, N. Trapp, O. Dumele, G. Klebe, F. Diederich, Chem. Eur. J. 2016, 22, 6750–6754. An Immucillin-based Transition State-Analogous Inhibitor of tRNA–Guanine Transglycosylase (TGT).
  16. G. Jayamurugan, V. Gowri, D. Hernández, S. Martin, C. Dengiz, O. Dumele, F. Pérez-Murano, J.-P. Gisselbrecht, C. Boudon, W. B. Schweizer, B. Breiten, A. D. Finke, G. Jeschke, B Bernet, L. Ruhlmann, P. Cea, F. Diederich, Chem. Eur. J. 2016, 22, 10539–10547. Design and Synthesis of Aviram-Ratner-Type Dyads and Rectification Studies in Langmuir-Blodgett (LB) Films.

Authors contributed equally.


Last update: August 2016