Comment on mr-2025-17

Abstract

Abstract. The copper(II) cages Pd12Cu6LDMAP24(Cu6) and Pd12Cu8LPro24 (Cu8), contain six, resp. eight, Cu(II) ions in a complex constituted by palladium ions and organic ligands in a self-assembled nano-meter sphere. Within the sphere, the Cu(II) ions are expected to form polyhedral-like structures. The parent compounds Pd12M6LDMAP24 and Pd12M8LPro24 are of interest because of the possibility of introducing a different metal ions for M, such as Cu(II), in a defined arrangement and for catalytic applications, see Bobylev et al. (Chemical Science, 2023, 14, 11840–11849). For structure information, nano-meter distances where measured between the six, respectively eight Cu(II) ions in Cu6 and Cu8. Distances were measured by pulsed double electron electron resonance (DEER) spectroscopy. While DEER is established for measuring distances between pairs of spins, application to multi-spin systems is less common. Since, so far, no reports of DEER with multi-spin interactions between Cu(II) ions were reported, the copper-cages are an ideal model to study them. For Cu6 and Cu8, DEER shows multi-spin interaction, and the method enabled to establish an octahedral arrangement for the Cu-ions in Cu6. For Cu8, two distances were observed that are consistent with two structural models proposed for Cu8, one of which is a cube of Cu-ions.

Authors 8

1. Leonardo Passerini Aachen Department of Physics, Leiden University Netherlands Huygens-Kamerlingh Onnes Laboratory

   Leiden University

   Affiliation as printed

   Department of Physics, Leiden University, the Netherlands Huygens-Kamerlingh Onnes Laboratory, Molecular Nano Optics and Spins, Leiden, 2333 CA, The Netherlands

2. Eduard Bobylev

   University of Amsterdam

   Affiliation as printed

   Van't Hoff institute for molecular sciences, University of Amsterdam, Amsterdam, 1090 GD, The Netherlands

3. Felix J. de Zwart

   University of Amsterdam

   Affiliation as printed

   Van't Hoff institute for molecular sciences, University of Amsterdam, Amsterdam, 1090 GD, The Netherlands

4. Henrik Hintz

   Bielefeld University

   Affiliation as printed

   Department of Chemistry, Bielefeld University, Bielefeld, D-33615, Germany

5. Adelheid Godt

   Bielefeld University

   Affiliation as printed

   Department of Chemistry, Bielefeld University, Bielefeld, D-33615, Germany

6. Bas de Bruin

   University of Amsterdam

   Affiliation as printed

   Van't Hoff institute for molecular sciences, University of Amsterdam, Amsterdam, 1090 GD, The Netherlands

7. Joost N. H. Reek

   University of Amsterdam

   Affiliation as printed

   Van't Hoff institute for molecular sciences, University of Amsterdam, Amsterdam, 1090 GD, The Netherlands

8. Martina Hüber corresponding

   University of Amsterdam

   Affiliation as printed

   Van't Hoff institute for molecular sciences, University of Amsterdam, Amsterdam, 1090 GD, The Netherlands