Abstract
The case of palladium(II) ions in molecular polyoxopalladates highlights the importance of accounting not only for nearest neighbour atoms or ions in order to understand, model or predict magnetic characteristics. Here, using site-specific soft X-ray magnetic circular dichroism (XMCD), the effects of different bond lengths, delocalization of 4d electrons, and 4d spin-orbit coupling on the electronic and magnetic properties are investigated and three different states identified: Conventional diamagnetism in a square-planar O4 coordination environment, paramagnetism caused by four additional out-of-plane oxygen anions, and an unusual diamagnetic state in the diamagnetic/paramagnetic crossover region modified by significant mixing of states and facilitated by the substantial 4d spin-orbit coupling. The two diamagnetic states can be distinguished by characteristic XMCD fine structures, thereby overcoming the common limitation of XMCD to ferro-/ferrimagnetic and paramagnetic materials in external magnetic fields. The qualitative interpretation of the results is corroborated by simulations based on charge transfer multiplet calculations and density functional theory results.
| Original language | English |
|---|---|
| Article number | 96 |
| Pages (from-to) | 1-10 |
| Journal | Communications Chemistry |
| Volume | 3 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 31 Jul 2020 |
Bibliographical note
Funding Information:We thank the Helmholtz-Zentrum Berlin (HZB) for the allocation of synchrotron radiation beamtime and access to the laboratory for magnetic measurements of the CoreLab Quantum Materials. For kind support we thank the HZB staff, particularly E. Weschke and E. Schierle. J. van Leusen (RWTH Aachen University) is gratefully acknowledged for additional magnetometry measurements and helpful discussions. This work was partly funded by the Helmholtz Association (Young Investigator’s Group Borderline Magnetism under contract no. VH-NG-1031).
Publisher Copyright:
© 2020, The Author(s).
Funding
We thank the Helmholtz-Zentrum Berlin (HZB) for the allocation of synchrotron radiation beamtime and access to the laboratory for magnetic measurements of the CoreLab Quantum Materials. For kind support we thank the HZB staff, particularly E. Weschke and E. Schierle. J. van Leusen (RWTH Aachen University) is gratefully acknowledged for additional magnetometry measurements and helpful discussions. This work was partly funded by the Helmholtz Association (Young Investigator’s Group Borderline Magnetism under contract no. VH-NG-1031).