Intramolecular crossover from unconventional diamagnetism to paramagnetism of palladium ions probed by soft X-ray magnetic circular dichroism

Smekhova A, Schmitz D, Izarova NV, Stuckart M, Shams SF, Siemensmeyer K, de Groot FM, Kögerler P, Schmitz-Antoniak C (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Communications Chemistry Nature Research

Book Volume: 3

Article Number: 96

Journal Issue: 1

DOI: 10.1038/s42004-020-0327-9

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.

Authors with CRIS profile

Maria Stuckart Lehrstuhl für Chemische Reaktionstechnik

Involved external institutions

Helmholtz-Zentrum Berlin für Materialien und Energie (HZB) DE Germany (DE) Forschungszentrum Jülich / Research Centre Jülich (FZJ) DE Germany (DE)

How to cite

APA:

Smekhova, A., Schmitz, D., Izarova, N.V., Stuckart, M., Shams, S.F., Siemensmeyer, K.,... Schmitz-Antoniak, C. (2020). Intramolecular crossover from unconventional diamagnetism to paramagnetism of palladium ions probed by soft X-ray magnetic circular dichroism. Communications Chemistry, 3(1). https://dx.doi.org/10.1038/s42004-020-0327-9

MLA:

Smekhova, Alevtina, et al. "Intramolecular crossover from unconventional diamagnetism to paramagnetism of palladium ions probed by soft X-ray magnetic circular dichroism." Communications Chemistry 3.1 (2020).

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