Chemistry Journal of Moldova

DOI: dx.doi.org/10.19261/cjm.2007.02(1).17

Graphical Abstract: In this paper we give a short overview of our efforts in the understanding of the magnetic properties of the fascinating nanoscopic cluster K₆[V^IV₁₅As₆O₄₂(H₂O)]·8H₂O (hereafter V15) exhibiting layers of magnetization. We analyze EPR and adiabatic magnetization of the V15 cluster with a triangular VIV3 array causing spin frustration. A model for V15 includes isotropic and antisymmetric (AS) exchange interactions in the general form compatible with the trigonal symmetry. Orientation of the AS vector (but not only its absolute value) is shown to play an important physical role in spin-frustrated systems. We were able to reach perfect fit to the experimental data on the stepwise dependence of magnetization vs. field at ultra-low temperatures. Furthermore, it was possible for the first time to estimate precisely two components of the AS vector coupling constant, namely, in-plane component and the perpendicular part. We show that only intramultiplet transitions in EPR are allowed when the vector of AS exchange is normal to the plane of vanadium triangle, meanwhile the in-plane part of AS exchange gives rise to a series of weak intermultiplet transitions. Experimental data on high-frequency EPR of V15 at low temperatures are discussed. The spin-vibronic effects in trimeric spin frustrated clusters are also studied and an important role of the interplay between the AS exchange and Jahn-Teller interaction is revealed. The results clarify the concept of spin-frustration in view of its magnetic and spectroscopic manifestations in metal clusters.


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