Ionic dynamics of the cation in organic–inorganic hybrid compound (CH3NH3)2MCl4(M = Cu and Zn) by1H MAS NMR,13C CP MAS NMR, and14N NMR

Lim, Ae Ran

doi:10.1039/c8ra02363h

Cited by 14 publications

(3 citation statements)

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“…NH 3 in the structure is correlated to CH 2 , and the main factor is a change in the surroundings of C−N groups in the [NH 3 (CH 2 ) 2 NH 3 ] cation. Remarkably, the changes in the 13 C and 14 N chemical shifts occurred around 300 K, and 1 H and 13 C T 1ρ exhibited maximum values near 300 K. From the DSC results, no phenomenon was observed at 300 K; however, the chemical shifts and T 1ρ results of 1 H, 13 C, and 14 N nuclei showed discontinuous changes around 300 K. From these results, we can infer that the surrounding environments of 1 H, 13 C, and 14 N sites change around 300 K. We compared the phase-transition temperatures, crystal structures, space groups, lattice constants, spin−lattice relaxation times, and activation energies of the previously reported (CH 3 NH 3 ) 2 ZnCl 4 32 with those of [NH 3 (CH 2 ) 2 NH 3 ]ZnCl 4 examined in this study, and the comparison results are summarized in Table 1. The difference between the two crystals lies only in the presence of organic cations.…”

Section: Discussionmentioning

confidence: 84%

“…We compared the phase-transition temperatures, crystal structures, space groups, lattice constants, spin–lattice relaxation times, and activation energies of the previously reported (CH 3 NH 3 ) 2 ZnCl 4 with those of [NH 3 (CH 2 ) 2 NH 3 ]ZnCl 4 examined in this study, and the comparison results are summarized in Table . The difference between the two crystals lies only in the presence of organic cations.…”

Section: Discussionmentioning

confidence: 99%

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Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH₃(CH₂)₂NH₃]ZnCl₄

Lim

2020

ACS Omega

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In this study, we investigated the structural dynamic features of the [NH3(CH2)2NH3]ZnCl4 crystal as a function of temperature through magic angle spinning (MAS) 1H nuclear magnetic resonance (NMR), MAS 13C NMR, and static 14N NMR. From the chemical shifts, changes in the structural environments of 13C and 14N were evident. The 1H spin–lattice relaxation time (T 1ρ) values at high temperatures undergo molecular motion according to the Bloembergen–Purcell–Pound theory, and the 13C T 1ρ value also varied abruptly with increasing temperature. Although the phase-transition temperature was not detected from the differential scanning calorimetry result, the chemical shifts and T 1ρ results showed discontinuities around 300 K. Herein, the activation energies of molecular motion for 1H and 13C obtained from T 1ρ are discussed. In addition, we compare the structural dynamics of diammonium-type [NH3(CH2)2NH3]ZnCl4 obtained in this study and monoammonium-type [CH3NH3]2ZnCl4 previously reported. The findings reported herein can provide important insights for potential applications of [NH3(CH2)2NH3]ZnCl4 crystals.

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Section: Discussionmentioning

confidence: 84%

Section: Discussionmentioning

confidence: 99%

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH₃(CH₂)₂NH₃]ZnCl₄

Lim

2020

ACS Omega

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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%

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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Structural phase transition, electrical and semiconducting properties in a lead‐free 2D hybrid perovskite‐like compound: [Cl‐(CH₂)₂‐NH₃]₂[CuCl₄]

Hajlaoui

Audebrand

Roisnel

et al. 2019

Applied Organom Chemis

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A new layered perovskite‐type organic–inorganic hybrid compound: [Cl‐(CH2)2‐NH3]2[CuCl4] (1), in which 2‐chloroethylammonium cation occupies the space enclosed by the CuCl6 octahedra, has been successfully synthesized. It is found that the compound exhibits the semiconducting properties with the optical band gap equal to 1.98 eV, confirmed by AC conductivity measurements, which varies between 10−5 and 10−4 Ω−1 m−1. Also, the low activation energy at low temperatures (0.26 eV) can indicate the electronic conduction of this material. Compound (1) displays phase transitions at T1 = 281 K and T2 = 380 K, confirmed by DSC, electrical and dielectric measurements. Single‐crystal X‐ray diffraction data at variable temperatures reveal that symmetry‐breaking occurs from P21/c (at 296 K ˃ T1) to P‐1 (at 150 K ˂ T1), originating directly from the [Cl‐(CH2)2‐NH3]+ cation conformational changes and the distortions of CuCl64− octahedra caused by the Jahn‐Teller effect in the inorganic layers. Meanwhile, organic 2‐chloroethylammonium moieties display some boat‐like conformation below T1, which transforms to a chair‐like structure above T1. This study paves the pathway to explore new lead‐free hybrid perovskites with targeted properties for thermoelectric, supercapacitors, batteries, environmentally friendly processing and semiconductor applications.

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Ionic dynamics of the cation in organic–inorganic hybrid compound (CH₃NH₃)₂MCl₄(M = Cu and Zn) by¹H MAS NMR,¹³C CP MAS NMR, and¹⁴N NMR

Abstract: The ionic dynamics of (CH3NH3)2MCl4 (M = Cu, Zn) by 1H MAS NMR, 13C CP MAS NMR, and 14N NMR are investigated as a function of temperature with a focus on the role of the CH3NH3+ cation.

Cited by 14 publications

References 41 publications

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH₃(CH₂)₂NH₃]ZnCl₄

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH₃(CH₂)₂NH₃]ZnCl₄

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

Structural phase transition, electrical and semiconducting properties in a lead‐free 2D hybrid perovskite‐like compound: [Cl‐(CH₂)₂‐NH₃]₂[CuCl₄]

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Ionic dynamics of the cation in organic–inorganic hybrid compound (CH3NH3)2MCl4(M = Cu and Zn) by1H MAS NMR,13C CP MAS NMR, and14N NMR

Abstract: The ionic dynamics of (CH3NH3)2MCl4 (M = Cu, Zn) by 1H MAS NMR, 13C CP MAS NMR, and 14N NMR are investigated as a function of temperature with a focus on the role of the CH3NH3+ cation.

Cited by 14 publications

References 41 publications

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH3(CH2)2NH3]ZnCl4

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH3(CH2)2NH3]ZnCl4

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

Structural phase transition, electrical and semiconducting properties in a lead‐free 2D hybrid perovskite‐like compound: [Cl‐(CH2)2‐NH3]2[CuCl4]

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Ionic dynamics of the cation in organic–inorganic hybrid compound (CH₃NH₃)₂MCl₄(M = Cu and Zn) by¹H MAS NMR,¹³C CP MAS NMR, and¹⁴N NMR

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH₃(CH₂)₂NH₃]ZnCl₄

Thermodynamic Properties, Structural Characteristics, and Cation Dynamics of Perovskite-Type Layer Crystal [NH₃(CH₂)₂NH₃]ZnCl₄

Structural phase transition, electrical and semiconducting properties in a lead‐free 2D hybrid perovskite‐like compound: [Cl‐(CH₂)₂‐NH₃]₂[CuCl₄]