How electron spin coupling affects catalytic oxygen activation

A team at the EPR4Energy joint lab of HZB and MPI CEC has developed a new THz EPR spectroscopy method to study the catalytic activation of molecular oxygen by copper complexes.

A team at the EPR4Energy joint lab of HZB and MPI CEC has developed a new THz EPR spectroscopy method to study the catalytic activation of molecular oxygen by copper complexes. © T. Lohmiller/HZB

A team at the EPR4Energy joint lab of HZB and MPI CEC has developed a new THz EPR spectroscopy method to study the catalytic activation of molecular oxygen by copper complexes. The method allows insights into previously inaccessible spin-spin interactions and the function of novel catalytic and magnetic materials.

 

Molecular oxygen (O2) is a preferred oxidant in green chemistry. However, activation of O2 and control of its reactivity requires precise adjustment of the spin states in the reactive intermediates. In nature, this is achieved by metalloenzymes that bind O2 at iron or copper ions, and spin-flip processes are enabled through metal-mediated spin-orbit couplings allowing for mixing of states. In the case of type III dicopper metalloproteins involved in oxygen transport and oxygenation of phenolic substrates, little was known about the pathway leading to a dicopper peroxo key species with a stabilized singlet ground state after triplet oxygen binding.

Through a sophisticated ligand design, the research group led by Prof. Franc Meyer at the University of Göttingen has now succeeded in isolating a series of model complexes that mimic the initial stage of oxygen binding at dicopper sites and exhibit a triplet ground state. Researchers from the EPR4Energy joint lab of HZB and MPI CEC complemented this breakthrough in chemical synthesis with a new approach of THz-EPR spectroscopy. This method, developed in Alexander Schnegg's group at MPI CEC, was applied for the first time to study the function-determining antisymmetric exchange in coupled dicopper(II) complexes.

The new method allowed for detection of the entirety of spin state transitions in the system, which leads to propose antisymmetric exchange as an efficient mixing mechanism for the triplet-to-singlet intersystem crossing in biorelevant peroxodicopper(II) intermediates. Thomas Lohmiller, one of the first authors of the study, explains, "In addition to the knowledge gained about this important system, our method opens up the possibility of studying previously inaccessible spin-spin interactions in a variety of novel catalytic and magnetic materials."

CEC/A. Schnegg

  • Copy link

You might also be interested in

  • New instrument at BESSY II: The OÆSE endstation in EMIL
    Science Highlight
    23.04.2025
    New instrument at BESSY II: The OÆSE endstation in EMIL
    A new instrument is now available at BESSY II for investigating catalyst materials, battery electrodes and other energy devices under operating conditions: the Operando Absorption and Emission Spectroscopy on EMIL (OÆSE) endstation in the Energy Materials In-situ Laboratory Berlin (EMIL). A team led by Raul Garcia-Diez and Marcus Bär showcases the instrument’s capabilities via a proof-of-concept study on electrodeposited copper.
  • Green hydrogen: A cage structured material transforms into a performant catalyst
    Science Highlight
    17.04.2025
    Green hydrogen: A cage structured material transforms into a performant catalyst
    Clathrates are characterised by a complex cage structure that provides space for guest ions too. Now, for the first time, a team has investigated the suitability of clathrates as catalysts for electrolytic hydrogen production with impressive results: the clathrate sample was even more efficient and robust than currently used nickel-based catalysts. They also found a reason for this enhanced performance. Measurements at BESSY II showed that the clathrates undergo structural changes during the catalytic reaction: the three-dimensional cage structure decays into ultra-thin nanosheets that allow maximum contact with active catalytic centres. The study has been published in the journal ‘Angewandte Chemie’.
  • An elegant method for the detection of single spins using photovoltage
    Science Highlight
    14.04.2025
    An elegant method for the detection of single spins using photovoltage
    Diamonds with certain optically active defects can be used as highly sensitive sensors or qubits for quantum computers, where the quantum information is stored in the electron spin state of these colour centres. However, the spin states have to be read out optically, which is often experimentally complex. Now, a team at HZB has developed an elegant method using a photo voltage to detect the individual and local spin states of these defects. This could lead to a much more compact design of quantum sensors.