Proton NMR study of spin dynamics in the magnetic organic chainsM(hfac)3NITEt(M=Eu3+,Gd3+)

Abstract

In this work, we present a nuclear magnetic resonance (NMR) study of the spin dynamics in the rare-earth-based low-dimensional molecular magnetic chains $\mathrm{Eu}{(\mathrm{hfac})}_{3}\mathrm{NITEt}$ and $\mathrm{Gd}{(\mathrm{hfac})}_{3}\mathrm{NITEt}$ (in short, Eu-Et and Gd-Et). Although both samples are based on the same chemical building block, [(${\mathrm{hfac})}_{3}\mathrm{NITEt}]$, their magnetic properties change dramatically when the ${\mathrm{Eu}}^{3+}$ ion, which is nonmagnetic at low temperatures, is substituted by the magnetic ${\mathrm{Gd}}^{3+}$ ion. The present proton NMR investigation shows that, down to the lowest investigated temperature ($T=1.5$ K for Gd-Et and $T=3$ K for Eu-Et), the Eu-Et chain behaves as a one-dimensional Heisenberg model with antiferromagnetic exchange coupling ($J=\ensuremath{-}20$ K) between $s=1/2$ organic radicals, and has a $T$-independent exchange frequency (${\ensuremath{\omega}}_{e}=2.6\ifmmode\times\else\texttimes\fi{}{10}^{12}$ rad/s). In the Gd-Et chain, in contrast, a competition arises between nearest-neighbor ferromagnetic coupling and next-nearest-neighbor antiferromagnetic coupling; moreover, two phase transitions have previously been found, in agreement with Villain's conjecture: a first transition, at ${T}_{0}=2.2$ K, from a high temperature paramagnetic phase to a chiral spin liquid phase, and a second transition, at ${T}_{N}=1.9$ K, to a three-dimensional helical spin solid phase. Contrary to the Eu-Et chain (whose three-dimensional ordering temperature is estimated to insurge at very low, ${T}_{N}\ensuremath{\approx}0.3$ K), critical spin dynamics effects have been measured in the Gd-Et chain on approaching ${T}_{N}=1.9$ K: namely, a divergence of the proton nuclear spin-lattice relaxation rate $1/{T}_{1}$, which in turn produces a sudden wipe-out of the NMR signal in a very narrow ($\mathrm{\ensuremath{\Delta}}T\ensuremath{\sim}0.04$ K) temperature range above ${T}_{N}$. Below ${T}_{N}$, an inhomogeneous broadening of the NMR line indicates a complete spin freezing. At ${T}_{0}=2.2$ K, instead, such critical effects are not observed because NMR measurements probe the two-spin correlation function, while the chiral spin liquid phase transition is associated with a divergence of the four-spin correlation function.