Thermal and structural properties, and molecular dynamics in organic–inorganic hybrid perovskite (C2H5NH3)2ZnCl4

Lim, Ae Ran

doi:10.1039/c9ra07695f

Cited by 3 publications

(3 citation statements)

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“…The relatively slow motion of Br-CH2-CH2 groups associated with changing the direction of the dipole moment of crystal 4 was detected by using a low-frequency AC electric field. The occupancy rate averages as the temperature increases from 106 K. The activation energy (Ea) for dielectric relaxation is 13.1 kJ mol -1 , which is comparable to those for molecular motion of ethyl groups in (CH3CH2NH3 + )[CuCl2] (21.13 kJ mol -1 ) and (CH3CH2NH3 + )[ZnCl2] (21.35 kJ mol -1 ), estimated by utilizing relaxation times in the solid-state13 C NMR 52,53. Similar responses of tan δ to temperature arising from X-CH2 motion occur in crystals 2 and 3.…”

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confidence: 79%

Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals

et al. 2021

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confidence: 79%

Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals

et al. 2021

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“…Indeed, the T 1ρ values are related to the corresponding values of the rotational correlation time, τ C , which is a direct measure of the rate of molecular motion. The experimental value of T 1ρ can therefore be expressed in terms of τ C for the molecular motion as suggested by the BPP theory [26,29,[31][32][33].…”

Section: Investigation Of the Structural Properties And Molecular Dynmentioning

confidence: 99%

“…The structures of (C 2 H 5 NH 3 ) 2 MCl 4 crystals with n = 2 are similar within each group but dissimilar between groups due to differences between either the inorganic or organic components. For example, the inorganic frames where M = Cu 2+ and Cd 2+ are Based on our previously reported nuclear magnetic resonance (NMR) results, the molecular dynamics of the cation present in (C 2 H 5 NH 3 ) 2 MCl 4 (M = Cu, Zn, and Cd) crystals were discussed in terms of temperature-dependent chemical shifts and spin-lattice relaxation times T 1ρ in the rotating frames for the 1 H and 13 C nuclei [25][26][27].…”

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confidence: 99%

Thermodynamic, Physical, and Structural Characteristics in Layered Hybrid Type (C2H5NH3)2MCl4 (M = 59Co, 63Cu, 65Zn, and 113Cd) Crystals

Lim

2020

Molecules

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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.Molecules 2020, 25, 1812 2 of 12 corner-sharing MCl 6 octahedra, while those of M = Co 2+ and Zn 2+ are simple MCl 4 tetrahedra [13]. In addition, the organic chains are joined by weak hydrogen bonds between the NH 3 groups and the Cl ions. Indeed, the structural geometries and molecular dynamics of the organic molecules within the layered hybrid structures are important for determining the influence of temperature on the structural phase transitions.As an example, (C 2 H 5 NH 3 ) 2 CoCl 4 crystallizes as an orthorhombic structure, which undergoes a reversible phase transition at 235 K [14]. In addition, (C 2 H 5 NH 3 ) 2 CuCl 4 undergoes phase transitions at 236, 330, 357, and 371 K [7,15-19], its crystal structure at room temperature is orthorhombic [20]. In contrast, (C 2 H 5 NH 3 ) 2 ZnCl 4 undergoes five phase transitions at 231, 234, 237, 247, and 312 K [21], crystallizing as an orthorhombic system at room temperature [22]. Finally, (C 2 H 5 NH 3 ) 2 CdCl 4 undergoes structural phase transitions at 114, 216, 358, and 470 K [9,23,24], whereby the room temperature orthorhombic phase has the Abma space group [23]. The structure of the organic component consists of a double layer of alkylammonium ions with the charged nitrogen atoms oriented to the nearest MCl 4 tetrahedra or MCl 6 octahedra. The phase transition temperatures, lattice constants, structures, and space groups for the four crystals are summarized in Table 1.

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Thermal property, structural characterization, and physical property of cation and anion in organic–inorganic perovskite [(CH2)3(NH3)2]CdCl4 crystal

Lim

2021

Journal of Solid State Chemistry

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Thermal and structural properties, and molecular dynamics in organic–inorganic hybrid perovskite (C₂H₅NH₃)₂ZnCl₄

Abstract: The thermal and structural properties and molecular dynamics of layered perovskite-type (C2H5NH3)2ZnCl4 are investigated by DSC, TGA, and MAS NMR spectroscopy.

Cited by 3 publications

References 25 publications

Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals

Molecular motion of halogenated ethylammonium/[18]crown-6 supramolecular ions in nickel dithiolate magnetic crystals

Thermodynamic, Physical, and Structural Characteristics in Layered Hybrid Type (C2H5NH3)2MCl4 (M = 59Co, 63Cu, 65Zn, and 113Cd) Crystals

Thermal property, structural characterization, and physical property of cation and anion in organic–inorganic perovskite [(CH2)3(NH3)2]CdCl4 crystal

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