Thermodynamic, Physical, and Structural Characteristics in Layered Hybrid Type (C(2)H(5)NH(3))(2)MCl(4) (M = (59)Co, (63)Cu, (65)Zn, and (113)Cd) Crystals

The thermal, physical, and molecular dynamics of layered hybrid type (C(2)H(5)NH(3))(2)MCl(4) (M = (59)Co, (63)Cu, (65)Zn, and (113)Cd) crystals were investigated by thermogravimetric analysis (TGA) and magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The temperatures of the onset of partial thermal decomposition were found to depend on the identity of M. In addition, the Bloembergen–Purcell–Pound curves for the (1)H spin-lattice relaxation time T(1ρ) in the rotating frames of CH(3)CH(2) and NH(3), and for the (13)C T(1ρ) of CH(3) and CH(2) were shown to exhibit minima as a function of the inverse temperature. These results confirmed the rotational motion of (1)H and (13)C in the C(2)H(5)NH(3) cation. Finally, the T(1ρ) values and activation energies E(a) obtained from the (1)H measurements for the H‒Cl···M (M = Zn and Cd) bond in the absence of paramagnetic ions were larger than those obtained for the H‒Cl···M (M = Co and Cu) bond in the presence of paramagnetic ions. Moreover, the E(a) value for (13)C, which is distant from the M ions, was found to decrease upon increasing the mass of the M ion, unlike in the case of the E(a) values for (1)H.