Pulsed ESR on the organic ion radical salt: 3,3′-diethyl-4,4′-dimethyl-2,2′-thiazolocyanine-[TCNQ]₂

Abstract

We present firstT ⁻¹_1e andT ⁻¹_2e measurements on the organic ion radical salt 3,3′-diethyl-4,4′-dimethyl-2,2′-thiazolocyanine-(TCNQ)₂ as function of temperature and of orientation. The electronic spin diffusion constant could be determined directly by the electron spin echo field gradient technique:D (300 K)=0.03±0.02 cm²/sec. Pulsed ESR experiments have — in comparison to conventional cw-ESR — the advantage to monitor viaT ⁻¹_1e andT ⁻¹_2e the spectral density of dynamical processes at different frequencies. This is shown in a general manner on 3,3′-diethyl-4,4′-dimethyl-2,2′-thiazolocyanine-(TCNQ)₂. Between 300 and 60 K,T ⁻¹_1e andT ⁻¹_2e are close in amplitude and have a similar temperature dependence. At 60 K their degeneracy is lifted, yielding a quantitative value for the effective spin exchange between localized spinsτ ⁻¹_ex sec⁻¹ and via the absolute value of the relaxation an average distance of the localized centers of about 12 Å. The dynamical data as evaluated above cannot be correlated with the conductivity, clearly indicating that the conduction electrons are a minority, not being monitored by the ESR-experiments.