Physicochemical properties and structural dynamics of organic–inorganic hybrid [NH3(CH2)3NH3]ZnX4 (X = Cl and Br) crystals

Abstract

The physical properties of the organic–inorganic hybrid crystals having the formula [NH3(CH2)3NH3]ZnX4 (X = Cl, Br) were investigated. The phase transition temperatures (TC; 268K for Cl and 272K for Br) of the two crystals bearing different halogen atoms in their skeletons were determined through differential scanning calorimetry. The thermodynamic properties of the two crystals were investigated through thermogravimetric analysis. The structural dynamics, particularly the role of the [NH3(CH2)3NH3] cation, were probed through 1H and 13C magic-angle spinning nuclear magnetic resonance spectroscopy as a function of temperature. The 1H and 13C NMR chemical shifts did not show any changes near TC. In addition, the 1H spin–lattice relaxation time (T1ρ) varied with temperature, whereas the 13C T1ρ values remained nearly constant at different temperatures. The T1ρ values of the atoms in [NH3(CH2)3NH3]ZnCl4 were higher than those in [NH3(CH2)3NH3]ZnBr4. The observed differences in the structural dynamics obtained from the chemical shifts and T1ρ values of the two compounds can be attributed to the differences in the bond lengths and halogen atoms. These findings can provide important insights or potential applications of these crystals.

Physicochemical Property Investigations of Perovskite-Type Layer Crystals [NH3(CH2)nNH3]CdCl4 (n = 2, 3, and 4) as a Function of Length n of CH2

“…The rectangular transparent single crystals were produced within 3–4 weeks, and these single crystals were stored in a desiccator to avoid moisture. The structures of the [NH 3 (CH 2 ) n NH 3 ]­CdCl 4 crystals at 298 K were analyzed using an X-ray diffraction system equipped with a Cu Kα radiation source . The lattice parameters were determined by single-crystal X-ray diffraction at the Seoul Western Center of the Korea Basic Science Institute (KBSI).…”

“…The lattice parameters were determined by single-crystal X-ray diffraction at the Seoul Western Center of the Korea Basic Science Institute (KBSI). The crystals were mounted on a Bruker D8 Venture equipped with a 1 μS microfocus sealed tube Mo Kα and a PHOTON III M14 detector …”

Phase transition, thermal stability, and molecular dynamics of organic–inorganic hybrid perovskite [NH3(CH2)6NH3]CuCl4 crystals

“…From the total molecular weight (Mw = 323.57 mg), the amount of residue was determined using eqn (1) and (2) . 37 {[NH 2 (CH 2 ) 6 NH 2 ·HCl]CuCl 4 + HCl (g) }/[NH 3 (CH 2 ) 6 NH 3 ]CuCl 4 = 88.73% {[NH 2 (CH 2 ) 6 NH 2 ]CuCl 4 + 2HCl (g) }/[NH 3 (CH 2 ) 6 NH 3 ]CuCl 4 = 77.46% …”

Effect of methylene chain length of perovskite-type layered [NH3(CH2)nNH3]ZnCl4 (n = 2, 3, and 4) crystals on thermodynamic properties, structural geometry, and molecular dynamics

“…The T 1 ρ values of the protons were 100–1000 ms, and these values decreased abruptly at 360 K. The values of E a for 1 H at low and high temperatures were 3.53 ± 0.02 and 31.86 ± 3.82 kJ mol −1 , respectively. 29 …”