Proton magnetic shielding and susceptibility effects in single crystals of ferrocene

The proton NMR in single crystals of ferrocene has been studied by multiple pulse techniques at room temperature. In crystals of natural shape with plane faces the angular dependence of the resonance frequency due to the anisotropy of the shielding and due to the bulk susceptibility was found to be of about equal size, making analysis of the data practically impossible. By using a single crystal sphere the shape dependent part of the susceptibility contribution could be eliminated. In addition, the resolution obtained by the multiple pulse technique is considerably higher for spheres than for non-spherical crystals. As the ferrocene molecules rotate rapidly about their fivefold axes at room temperature, the shielding tensor σ must be axially symmetric. Having this in mind, the data could be analyzed to yield both the shielding tensor with Δσ = σ₆ - σ_⊥ = ?6.5 ± 0.1 ppm, σ_iso = ?4.2 ± 0.5 ppm from a spherical sample of TMS and the anisotropy of the susceptibility Δ _x = 30 × 10^?6 cgs units.