Magnetic properties and hyperfine interactions in Cr8, Cr7Cd, and Cr7Ni molecular rings from 19F-NMR

A detailed experimental investigation of the 19F nuclear magnetic resonance is made on single crystals of the homometallic Cr8 antiferromagnetic molecular ring and heterometallic Cr7Cd and Cr7Ni rings in the low temperature ground state. Since the F - ion is located midway between neighboring magnetic metal ions in the ring, the 19F-NMR spectra yield information about the local electronic spin density and 19F hyperfine interactions. In Cr 8, where the ground state is a singlet with total spin ST = 0, the 19F-NMR spectra at 1.7 K and low external magnetic field display a single narrow line, while when the magnetic field is increased towards the first level crossing field, satellite lines appear in the 19F-NMR spectrum, indicating a progressive increase in the Boltzmann population of the first excited state ST = 1. In the heterometallic rings, Cr7Cd and Cr7Ni, whose ground state is magnetic with ST = 3/2 and ST = 1/2, respectively, the 19F-NMR spectrum has a complicated structure which depends on the strength and orientation of the magnetic field, due to both isotropic and anisotropic transferred hyperfine interactions and classical dipolar interactions. From the 19F-NMR spectra in single crystals we estimated the transferred hyperfine constants for both the F--Ni 2+ and the F--Cd2+ bonds. The values of the hyperfine constants compare well to the ones known for F--Ni 2+ in KNiF3 and NiF2 and for F --Cr3+ in K2NaCrF6. The results are discussed in terms of hybridization of the 2s, 2p orbitals of the F- ion and the d orbitals of the magnetic ion. Finally, we discuss the implications of our results for the electron-spin decoherence.