Dr. Alexander Schnegg - EPR Research Group

Dr. Alexander Schnegg
Head of Group EPR Research Group

Vita

Dipl.-Phys. Free University Berlin (1998)
Dr. rer. nat.Institut für Experimentalphysik, Free University Berlin (1999-2003)
PostdocMax Planck Institute for Bioinorganic Chemistry; today: MPI CEC (2004-2005)
PostdocHelmholtz Zentrum Berlin für Materialien und Energie (HZB) (2006-2013)
Staff ScientistHZB's EPR lab (2013-2018)
Adjunct ProfessorMonash University, Melbourne, Australia (since 2016)
Research group leaderMPI CEC (since 2018)

Publications

Full publications list

Selected MPI CEC publications

  • Pavlov, A.A., Nehrkorn, J., Zubkevich, S.V., Fedin, M.V., Holldack, K., Schnegg, A., Novikov, V.V. (2020). A Synergy and Struggle of EPR, Magnetometry and NMR: A Case Study of Magnetic Interaction Parameters in a Six-Coordinate Cobalt(II) Complex Inorganic Chemistry 59(15), 10746-10755. https://doi.org/10.1021/acs.inorgchem.0c01191
  • Viciano-Chumillas, M., Blondin, G., Clémanceym N., Krzystek, J., Ozerov, M., Armentano, D., Schnegg, A., Lohmiller, T., Telser, J., Lloret, F., Cano, J. (2020). Single‐Ion Magnetic Behaviour in an Iron(III) Porphyrin Complex: A Dichotomy Between High‐Spin and 5/2−3/2 Spin Admixture Chemistry – A European Journal https://doi.org/10.1002/chem.202003052
  • Jochim, A., Lohmiller, T., Rams, M., Böhme, M., Ceglarska, M., Schnegg, A., Plass, W., Näther, C. (2020). Influence of the Coligand onto the Magnetic Anisotropy and the Magnetic Behavior of One-Dimensional Coordination Polymers Inorganic Chemistry 59(13), 8971-8982. https://doi.org/10.1021/acs.inorgchem.0c00815
  • Lin, Y.-H., Kutin, Y., van Gastel, M., Bill, E., Schnegg, A., Ye, S., Lee, W.-Z. (2020). A Manganese(IV)-Hydroperoxo Intermediate Generated by Protonation of the Corresponding Manganese(III)-Superoxo Complex Journal of the American Chemical Society https://doi.org/10.1021/jacs.0c02756
  • Böhme, M., Jochim, A., Rams, M., Lohmiller, T., Suckert, S., Schnegg, A., Plass, W., Näther, C. (2020). Variation of the Chain Geometry in Isomeric 1D Co(NCS)2 Coordination Polymers and Their Influence on the Magnetic Properties Inorganic Chemistry 59(8), 5325-5338. https://doi.org/10.1021/acs.inorgchem.9b03357
  • Ma, Y., Pang, Y., Chabbra, S., Reijerse, E.J., Schnegg, A., Niski, J., Leutzsch, M., Cornella, J. (2020). Radical C‒N Borylation of Aromatic Amines Enabled by a Pyrylium Reagent Chemistry – A European Journal 26(17), 3734-3743. https://doi.org/10.1002/chem.202000412
  • Krzystek, J., Schnegg, A., Aliabadi, A., Holldack, K., Stoian, S.A., Ozarowski, A., Hicks, S.D., Abu Omar, M.M., Thomas, K.E., Ghosh, A., Caulfield, K.P., Tonzetich, Z.J., Telser, J. (2020). Advanced Paramagnetic Resonance Studies on Manganese and Iron Corroles with a Formal d4 Electron Count Inorganic Chemistry 59(2), 1075-1090. https://doi.org/10.1021/acs.inorgchem.9b02635
  • Li, J., Chen, J., Sang, R., Ham, W.-S., Plutschack, M.B., Berger, F., Chabbra, S., Schnegg, A., Genicot, C., Ritter, T. (2020). Photoredox catalysis with aryl sulfonium salts enables site-selective late-stage fluorination Nature Chemistry 12, 56-62. https://doi.org/10.1038/s41557-019-0353-3
  • Rams, M., Jochim, A., Böhme, M., Lohmiller, T., Ceglarska, M., Rams, M.M., Schnegg, A., Plass, W., Näther, C. (2020). Single‐Chain Magnet Based on Cobalt(II) Thiocyanate as XXZ Spin Chain Chemistry – A European Journal 26(13), 2837-2851. https://doi.org/10.1002/chem.201903924
  • Kutin, Y., Cox, N., Lubitz, W., Schnegg, A., Rüdiger, O. (2019). In Situ EPR Characterization of a Cobalt Oxide Water Oxidation Catalyst at Neutral pH Catalysts 9(11), 926. https://doi.org/10.3390/catal9110926
  • Nehrkorn, J., Bonke, S.A., Aliabadi, A., Schwalbe, M., Schnegg, A. (2019). Examination of the Magneto-Structural Effects of Hangman Groups on Ferric Porphyrins by EPR Inorganic Chemistry 58(20), 14228-14237. https://doi.org/10.1021/acs.inorgchem.9b02348
  • Sidabras, J., Duan, J., Winkler, M., Happe, T., Hussein, R., Zouni, A., Suter, D., Schnegg, A., Lubitz, W., Reijerse, E.J. (2019) Extending electron paramagnetic resonance to nanoliter volume protein single crystals using a self-resonant microhelix Science Advances 5(10), eaay1394. https://doi.org/10.1126/sciadv.aay1394
  • Cheng, J., Liu, J., Leng, X., Lohmiller, T., Schnegg, A., Bill, E., Ye, S., Deng, L. (2019). A Two-Coordinate Iron(II) Imido Complex with NHC Ligation: Synthesis, Characterization, and Its Diversified Reactivity of Nitrene Transfer and C–H Bond Activation Inorganic Chemistry 58, 7634-6744. https://doi.org/10.1021/acs.inorgchem.9b01147
  • Zhao, G., Busser, G.W., Froese, C., Hu, B., Bohnke, S.A., Schnegg, A., Ai, Y., Wei, D., Wang, X., Peng, B., Muhler, M. (2019). Anaerobic Alcohol Conversion to Carbonyl Compounds Over Nanoscaled Rh-doped SrTiO3 under Visible Light The Journal of Physical Chemistry Letters 10, 2075–2080. https://doi.org/10.1021/acs.jpclett.9b00621
  • Nehrkorn, J., Veber, S.L., Zhukas, L.A., Novikov, V.N., Nelyubina, Y.V., Voloshin, Y.Z, Holldach, K., Stoll, S., Schnegg, A. (2018). Determination of Large Zero-Field Splitting in High-Spin Co(I) Clathrochelates Inorganic Chemistry 57(24), 15330-15340. https://doi.org/10.1021/acs.inorgchem.8b02670



Group members

Group leaders (Deputies)

  • Dr. Edward J. Reijerse

laboratory coordinator

  • Dr. Leonid Rapatskiy

Postdocs

  • Dr. Shannon Bonke
  • Dr. Sonia Chabbra
  • Dr. Yury Kutin (Guest)
  • Dr. Joscha Paul Nehrkorn
  • Jason W. Sidabras
  • Dr. Markus Teucher

PhD students

  • Stephany Natasha Arellano Ahumada (Guest)

EPR Research Group @ MPI CEC

The EPR Research Group at MPI CEC employs electron paramagnetic resonance (EPR) techniques to monitor and characterize paramagnetic states relevant to energy conversion and storage processes. Special focus is devoted to catalytically active transition metal ion complexes and radicals. We develop and utilize state-of-the-art EPR spectrometers ranging from GHz to THz frequencies. Our spectrometers are capable of a wide repertoire of CW/pulsed multi-resonance and multi-frequency EPR methods for powder, crystal, solution and in situ experiments.

Currently we are working in the following fields of research:

In-situ EPR

An understanding of catalyst function enables rational modification and improvement. Yet, the most reactive and catalytically active states are typically only formed under operational conditions. This motivates our group to develop methodology for in situ / operando studies that allow EPR characterization of catalysts for energy conversion reactions. These studies require electrochemical measurements to be undertaken within the constraints of specific spectroscopic equipment, which we design and develop to ensure the conditions of analysis are truly relevant to the operational catalytic activity.

The applicability of EPR to any electrochemically derived/analyzed species is that single electron redox steps frequently involve paramagnetic states. The exceptional sensitivity of EPR to these states makes it powerful in examining the subtle, but crucial, electronic effects that enable catalysis. EPR also allows selective analysis of paramagnetic oxidation states independent of diamagnetic species, thus providing selectivity that is unavailable with many other techniques - especially if the catalyst ground state is diamagnetic. In situ EPR spectra are interpreted with extensive experiment-simulation comparisons and then correlated with catalytic measurements as well as with results from other techniques.

Contact: Shannon Bonke and Sonia Chabbra

High-spin transition metal ion states

EPR characterization of high-spin (electron spin, S > 1/2) transition-metal ion states targets the determination of their spin coupling parameters. The latter are sensitive probes of the coordination environment and electronic structure of the metal ion. In the case of catalytically active ions, spin couplings can provide unique information on their structure-function relationship. Furthermore, spin couplings determine the magnetic properties of molecular nanomagnets (MNM), which are considered as core units of future spintronic devices. However, the highly desired spin couplings are oftentimes not accessible with standard EPR spectrometers. This is the case for many high spin states with large zero field splittings. To improve this situation we develop and apply advanced field and frequency domain EPR methods, covering the GHz to THz EPR-excitation energy range. For THz-EPR experiments the Schnegg group established the joint research lab EPR4Energy with the the Helmholtz-Zentrum Berlin für Materialien und Energie (HZB).
Collaboration partners: Prof. Robert Bittl (FU Berlin), Dr. Karsten Holldack and Dr. Thomas Lohmiller (both HZB, Berlin).

Contact: Joscha Nehkorn

1.    Nehrkorn, J.; Holldack, K.; Bittl, R.; Schnegg, A., J. Magn. Reson. 2017, 280, 10-19.

Metalloproteins

Paramagnetic states of metal proteins are studied by high-resolution multi-frequency and multi-resonance EPR techniques. Nuclear spins (e.g. 14/15N, 13C) of the first coordination sphere ligands (e.g. CN and CO) are used as reporters on the spin density distribution over a metal cluster. The latter can be probed by hyperfine spectroscopies (in our lab we use, ENDOR, HYSCORE and EDNMR), which allow determination of the hyperfine and quadrupole interactions. Optimum conditions for such experiments are achieved by single crystal EPR measurements. However, protein micro-crystals have typical sizes in the range 50 – 200 µm. Even at W-band, EPR investigation of these crystals is challenging. To lift this restriction, our group develops resonant structures adapted to the size and shape of nanoliter volume samples at X-, Q-, and W-band (9.5, 34, and 94 GHz respectively) up to the sub mm (244 GHz) and THz range.  In order to significantly advance EPR spectroscopy for samples with nanolitre volumes, a novel sub-mm sized X-band self-resonant micro-helix resonator has been developed in collaboration with Prof. Lubitz (see Fig. 4). The sensitivity enhancement obtained with this resonator makes protein single crystals of dimensions typical for x-ray crystallography accessible to advanced EPR techniques.

Contact: Ed Reijerse and Jason Sidabras

2.    Sidabras, J. W.; Duan, J.; Winkler, M.; Happe, T.; Hussein, R.; Zouni, A.; Suter, D.; Schnegg, A.; Lubitz, W.; Reijerse, E. J., Science Advances 2019, 5 (10), eaay1394.

EPR-on-a-Chip (EPRoC)

EPRoC are mm-sized sensors that incorporate a microwave source and detector on a surface array. This approach allows for a fundamental paradigm shift in EPR spectroscopy by facilitating in situ measurements of paramagnetic samples in environments which are difficult to access with conventional EPR setups in a cost-efficient way. We are developing EPR detection schemes that employ EPRoC sensors in a variety of different environments probing a wide range of sample morphologies in the scope of catalysis and battery research. We work on their integration in electrodes of electrochemistry experiments for the characterization of paramagnetic states in liquid solutions, e.g. in electrochemical cells, batteries or reactors. In addition, we are developing rotation-dependent EPRoC techniques for studies of microcrystals. The current generation of EPRoC sensors is capable of performing continuous wave and rapid scan EPR experiments. Partners: Prof. Dr. Klaus Lips (HZB), Prof. Jens Anders (Universität Stuttgart). Sponsored by the Federal Ministry of Education and Research (Grant reference number: 03SF0565A).

Contact: Markus Teucher