Exploring the potential applications of lead-free organic-inorganic perovskite type [NH3(CH2)nNH3]MCl4 (n = 2, 3, 4, 5, and 6; M = Mn, Co, Cu, Zn, and Cd) crystals.

The organic-inorganic hybrid perovskite compounds have been extensively studied since the dawn of a new era in the field of photovoltaic applications. Up to now, perovskites have proven to be the most promising in terms of power conversion efficiency; however, their main disadvantages for use in solar cells are toxicity and chemical instability. Therefore, it is essential to develop a hybrid perovskite that can be replaced with lead-free materials. This review focuses on the possibility of applying lead-free organic-inorganic perovskite types [NH3(CH2)nNH3]MCl4 (n = 2, 3, 4, 5, and 6; M = Mn, Co, Cu, Zn, and Cd) crystals. We are seeking organic-inorganic hybrid perovskite materials with very high temperature stability or without phase transition temperature, and thermal stability. Thus, by considering the characteristics according to the methylene lengths and the various transition metals, we aim to identify improved materials meeting the criteria mentioned above. Consequently, the physicochemical properties of organic-inorganic hybrid perovskite [NH3(CH2)nNH3]MCl4 regarding the effects of various transition metal ions of the anion and the methylene lengths of the cation are expected to promote the development and application of lead-free hybrid perovskite solar cells.

NMR analysis of structural geometry and molecular dynamics in perovskite-type N(CH3)4CdBr3 crystal near high-temperature phase transition.

The NMR chemical shifts, linewidths, spin-lattice relaxation times in the rotating system T1ρ, and spin-lattice relaxation times in the laboratory system T1 were evaluated for the perovskite-type N(CH3)4CdBr3 crystal, aiming to understand the changes in the structural geometry and molecular dynamics from phase I to phase II. From the temperature-dependence of the 1H, 13C, 14N, and 113Cd NMR chemical shifts, the structural geometry underwent a continuous change, without anomalous changes around (TC = 390 K). However, the linewidths in phase I were narrower than those in phase II, indicating that the motional averaging effects were caused by the rapid rotation of the N(CH3)4 group. Sudden changes in T1 and T1ρ were observed near TC, for which the activation energy Ea in phase I was approximately 12 times larger than that in phase II; the small Ea values in phase II indicate a large degree of freedom for the methyl group and CdBr6 octahedra, whereas the large Ea in phase I was primarily attributed to the overall N(CH3)4 and the 113Cd in the CdBr6 groups. Consequently, the phase transition mechanisms of N(CH3)4CdBr3 are related to reorientation of the N(CH3)4 group and the arrangement of the CdBr6 groups.

Crystal structures, phase transitions, thermodynamics, and molecular dynamics of organic-inorganic hybrid crystal [NH(CH3)3]2ZnCl4.

Understanding the physical properties of organic-inorganic hybrid [NH(CH3)3]2ZnCl4 is necessary for its potential application in batteries and fuel cells due to its environmentally-friendly, and highly stable character. Here, we determine its overall properties in detail, such as its orthorhombic crystal structure, and phase transition temperatures associated with five different phases. Structural geometry was studied by the chemical shifts caused by the local field around 1H. No changes were observed for the environment around 1H for CH3, whereas the 1H chemical shifts around NH in the cation were shown due to the change in the hydrogen bond N‒H···Cl. This is related to the change in Cl around Zn in the anion. In addition, the coordination geometry of 14N and 1H around 13C exhibited increased symmetry at high temperatures. Finally, we were able to understand its molecular dynamics by the significant change with temperature observed from the spin-lattice relaxation time T1ρ values, which represent the energy transfer for the 1H and 13C atoms of the cation. The activation energies obtained from the T1ρ results were 3-4 times large at phase I (> 348 K) than at phase V and IV (< 286 K). The relaxations show that the energy barriers in phases IV and V are related to the reorientation of methyl groups around the triple symmetry axis, while the reorientation of methyl groups of the cation in phase I is related to as a whole.

Investigation on the organic-inorganic hybrid crystal [NH2(CH3)2]2CuBr4: structure, phase transition, thermal property, structural geometry, and dynamics.

Understanding the physical properties of the organic-inorganic hybrid [NH2(CH3)2]2CuBr4 is essential to expand its applications. The single [NH2(CH3)2]2CuBr4 crystals were grown and their comprehensive properties were investigated. The crystals had a monoclinic structure with the space group P21/n and lattice constants of a = 8.8651 (5) Å, b = 11.9938 (6) Å, c = 13.3559 (7) Å, and ß = 91.322°. The transition temperature from phase I to phase II was determined to be 388 K. Variations in the 1H nuclear magnetic resonance chemical shifts of NH2 and 14N NMR chemical shifts according to the temperature changes in the cation were attributed to vibrations of NH2 groups at their localization sites. The 1H and 13C spin-lattice relaxation times (T1ρ) in phase II changed significantly with temperature, indicating that these values are governed by molecular motion. The T1ρ values were much longer in phase I than in phase II, which means energy transfer was difficult. Finally, the activation energies for phases I and II were considered. According to the basic mechanism of [NH2(CH3)2]2CuBr4 crystals, organic-inorganic materials may have potential applications in various fields.

Processing on crystal growth, structure, thermal property, and nuclear magnetic resonance of organic-inorganic hybrid perovskite type [NH3(CH2)6NH3]ZnCl4 crystal.

Organic-inorganic hybrid compounds have recently gained significant attention in recent years due to their diverse applications. Herein, [NH3(CH2)6NH3]ZnCl4 crystals were grown, and their triclinic structure, phase transition temperature (TC = 408 K), and high thermal stability (Td = 584 K) was determined using X-ray diffraction (XRD), differential scanning calorimetry, and thermogravimetry measurements. By analyzing the chemical in response to temperature changes, we observed that the coordination geometry around 1H and 13C were highly symmetric below TC, whereas their symmetry was lowered above TC. The change of N-H⋯Cl hydrogen bond from XRD results and the change of 14N NMR chemical shifts was due to the changes to the coordination geometry of Cl- around Zn2+ in the ZnCl4 anion. The activation energy of 1H was three times greater than that of 13C, and this result indicates that the energy transfer of 13C was easier than those of 1H. We compared the results for [NH3(CH2)nNH3]ZnCl4 (n = 6) studied here with those for n = 2, 3, 4, and 5 obtained from previous studies. The characteristics of the length of CH2 in the methylene chain are expected to be used for potential applications in the near future.

Analysis of the Structure, Thermal, and Molecular Dynamics of Organic-Inorganic Hybrid Crystal at Phases IV, III, II, and I: [NH2(CH3)2]2CdBr4.

A comprehensive understanding of the physicochemical properties of organic-inorganic hybrids is essential for their solid-state lighting applications. Therefore, a single crystal of [NH2(CH3)2]2CdBr4 was grown; the crystal structure was monoclinic, and the phase transition temperatures for the four phases IV, III, II, and I were 383 K (TC1), 417 K (TC2), and 427 K (TC3). Furthermore, the chemical shifts caused by the local field around 1H, 13C, 14N, and 113Cd changed continuously with temperature, especially near TC1, indicating that the local environment changes with temperature. Owing to the large change in 113Cd chemical shifts, the coordination geometry of Br around Cd in the CdBr4 tetrahedra changes near TC1. Therefore, it is proposed that Br plays a significant role in the N-H···Br hydrogen bond. Finally, the spin-lattice relaxation time T1ρ, representing the energy transfer around the 1H and 13C atoms of the cation, changed significantly with temperature. The activation energies obtained from the T1ρ results were two times larger at high temperatures than at low temperatures. This study provides an understanding of the fundamental properties of organic-inorganic hybrid compounds to broaden their applications.

Crystal growth, phase transition, and nuclear magnetic resonance of organic-inorganic hybrid perovskite NH2(CH3)2CdCl3.

Understanding the physicochemical properties of organic-inorganic hybrid materials is essential to promote their applications. In this study, a single crystal of NH2(CH3)2CdCl3 was grown, and it exhibited a monoclinic structure. Its phase transition temperatures were 460 and 470 K, and it showed sufficient thermal stability. The changes in the NMR chemical shifts of each atom in the crystal with increasing temperature were determined; the chemical shift of 1H of NH2 in the NH2(CH3)2 cation changed with temperature, which was correlated to the changes in the chemical shift of 14N in NH2. The change in 113Cd chemical shifts indicate the change of six Cl atoms around Cd in CdCl6. Therefore, the change in the coordination geometry of CdCl6 is attributed to the change in the N-H⋯Cl hydrogen bond between the NH2(CH3)2 cation and CdCl6 anion. In addition, the 13C activation energies Ea obtained from the spin-lattice relaxation time T1ρ values are smaller than those of the 1H Ea values, suggesting that is free compared to 1H in the cation. We believe that this study furthers our fundamental understanding of organic-inorganic hybrid materials to promote their practical solar cell applications.

Investigation of the structure, phase transitions, molecular dynamics, and ferroelasticity of organic-inorganic hybrid NH(CH3)3CdCl3 crystals.

Understanding the physical and chemical properties of the organic-inorganic hybrid NH(CH3)3CdCl3 is essential for its application. Considering its importance, a single crystal of NH(CH3)3CdCl3 was grown with an orthorhombic structure at 300 K. The phase transition temperatures were determined to be 345 (TC3), 376 (TC2), and 452 K (TC1) (phases IV, III, II, and I, respectively, starting from a low temperature). The partial decomposition temperature was 522 K (Td). Furthermore, the NMR chemical shifts of the 1H, 13C, and 113Cd atoms of the cation and anion varied with increasing temperature. Consequently, a significant change in the coordination geometry of Cl around Cd in CdCl6 and a change in the coordination geometry of H in NH was associated with changes in the N-H⋯Cl hydrogen bond near the phase transition temperature. The 13C activation energy Ea obtained from the spin-lattice relaxation time was smaller than that of 1H Ea, suggesting that energy transfer around 13C is easier. Additionally, a comparison of the twin domain walls measured via optical polarizing microscopy and Sapriel's theory indicated that the crystal structure in phase III was more likely to be orthorhombic than hexagonal.

Investigating the physicochemical properties, structural attributes, and molecular dynamics of organic-inorganic hybrid [NH3(CH2)2NH3]2CdBr4·2Br crystals.

An in-depth understanding of the physicochemical properties of the organic-inorganic hybrid [NH3(CH2)2NH3]2CdBr6 whose structure corresponds to the formulation [NH3(CH2)2NH3]2CdBr4· 2Br is essential for its application in batteries, supercapacitors, and fuel cells. Therefore, this study aimed to determine the crystal structure, phase transition, structural geometry, and molecular dynamics of these complexes. Considering its importance, a single crystal of [NH3(CH2)2NH3]2CdBr6 was grown; the crystal structure was found to be monoclinic. The phase transition temperatures were determined to be 443, 487, 517, and 529 K, and the crystal was thermally stable up to 580 K. Furthermore, the 1H, 13C, 14N, and 113Cd NMR chemical shifts caused by the local field surrounding the resonating nucleus of the cation and anion varied with increasing temperature, along with the surrounding environments of their atoms. In addition, 1H spin-lattice relaxation time T1ρ and 13C T1ρ, which represent the energy transfer around the 1H and 13C atoms of the cation, respectively, varied significantly with temperature. Consequently, changes in the coordination geometry of Br around Cd in the CdBr6 anion and the coordination environment around N (in the cation) were associated with changes in the N-H···Br hydrogen bond. The structural geometry revealed critical information regarding their basic mechanism of organic-inorganic hybrid compounds.

Crystal structures, phase transitions, and nuclear magnetic resonance of organic-inorganic hybrid [NH2(CH3)2]2ZnBr4 crystals.

Organic-inorganic hybrid [NH2(CH3)2]2ZnBr4 crystals were grown via slow evaporation, and their monoclinic structure was determined using single-crystal X-ray diffraction (XRD). The two phase transition temperatures at 401 K (T C1) and 436 K (T C2) were defined using differential scanning calorimetry and powder XRD. In the nuclear magnetic resonance spectra, a small change was observed in the 1H chemical shifts for NH2, 13C chemical shifts for CH3, and 14N resonance frequency for NH2 near T C1. 1H spin-lattice relaxation times T 1ρ and 13C T 1ρ for NH2 and CH3, respectively, rapidly decreased near T C1, suggesting that energy was easily transferred. NH2 in the [NH2(CH3)2]+ cation was significantly influenced by the surrounding environments of 1H and 14N, indicating a change in the N-H⋯Br hydrogen bond with the coordination geometry of the ZnBr4 anion. These fundamental properties open efficient avenues for the development of organic-inorganic hybrids, thus qualifying them for practical applications.

Comparison of the properties of polyimide nanocomposite films containing functionalized-graphene and organoclay as nanofillers.

Poly(amic acid) (PAA) is prepared by the reaction of dianhydride 4,4'-biphthalic anhydride and diamine bis[4-(3-aminophenoxy)phenyl]sulfone in N,N'-dimethylacetamide. Two types of fillers were dispersed in the as-synthesized PAA via a solution intercalation method; polyimide (PI) hybrid films were synthesized under various heat treatment conditions. Octylamine (C8) was introduced into graphene sheets (C8-GS) and bentonite (C8-BTN), which were then used as nanofillers in the PI hybrid films. The synthesized nanofillers were used in varying amounts of 0.25-1.00 wt% with respect to the matrix PI. The thermal and morphological properties and optical transparency of the hybrid films were investigated and compared for both C8-GS and C8-BTN at varying nanofiller content. The C8-BTN nanocomposite showed superior thermal properties, and optical transparency, and the filler was well dispersed in the PI matrix compared to the C8-GS nanocomposite. The thermal stability of the hybrid films improved upon the addition of small amounts of the nanofiller. However, beyond a certain critical filler concentration, the thermal stability declined. These results were verified through the dispersion of fillers via transmission electron microscopy.

Organic-inorganic hybrid [NH3(CH2)6NH3]ZnBr4 crystal: structural characterization, phase transitions, thermal properties, and structural dynamics.

Organic-inorganic hybrid [NH3(CH2)6NH3]ZnBr4 crystals were prepared by slow evaporation; the crystals had a monoclinic structure with space group P21/c and lattice constants a = 7.7833 Å, b = 14.5312 Å, c = 13.2396 Å, ß = 90.8650°, and Z = 4. They underwent two phase transitions, at 370 K (T C1) and 430 K (T C2), as confirmed by powder X-ray diffraction patterns at various temperatures; the crystals were stable up to 600 K. The nuclear magnetic resonance spectra, obtained using the magic-angle spinning method, demonstrated changes in the 1H and 13C chemical shifts were observed near T C1, indicating changing structural environments around 1H and 13C. The spin-lattice relaxation time, T 1ρ, increased rapidly near T C1 suggesting very large energy transfer, as indicated by a large thermal displacement around the 13C atoms of the cation. However, the environments of 1H, 14N, and C1 located close to NH3 in the [NH3(CH2)6NH3] cation did not influence it significantly, indicating a minor change in the N-H⋯Br hydrogen bond with the coordination geometry of the ZnBr4 anion. We believe that the information on the physiochemical properties and thermal stability of [NH3(CH2)6NH3]ZnBr4, as discussed in this study, would be key to exploring its application in stable, environment friendly solar cells.

Growth, structure, phase transition, thermal properties, and structural dynamics of organic-inorganic hybrid [NH3(CH2)5NH3]ZnCl4 crystal.

In this study, the physicochemical properties of [NH3(CH2)5NH3]ZnCl4 crystals were investigated using X-ray diffraction (XRD), Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, and nuclear magnetic resonance (NMR). The crystals at 300 K had a monoclinic structure with C2/c space group and lattice constants are a = 21.4175 Å, b = 7.3574 Å, c = 19.1079 Å, ß = 120.5190°, and Z = 8. Three endothermic peaks at 256, 390, and 481 K were observed in the DSC curve. From the single-crystal XRD patterns, powder XRD patterns, and optical microscopy results based on the temperature change, the phase transition and melting temperatures were determined to be 390 and 481 K, respectively. NMR studies indicated no change in 1H chemical shifts, but a change in the chemical shifts for C2, located between C1 and C3 of the cation at 340 K. Increase in molecular motion caused an increase in the spin-lattice relaxation time, T1ρ, at low spinning rates, under magic-angle spinning rate conditions. This crystal showed a minor change in the N-H···Cl hydrogen bond, related to the coordination geometry of the ZnCl4 anion.

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

Organic-inorganic hybrid perovskites have various potential applications in fuel cells and solar cells. In this regard, the physicochemical properties of an organic-inorganic [NH3(CH2)6NH3]CuCl4 crystal was conducted. The crystals had a monoclinic structure with space group P21/n and lattice constants a = 7.2224 Å, b = 7.6112 Å, c = 23.3315 Å, ß = 91.930°, and Z = 4 at 300 K, and the phase transition temperature (T C) was determined to be 363 K by X-ray diffraction and differential scanning calorimetry experiments. From the nuclear magnetic resonance experimental results, the changes in the 1H chemical shifts in NH3 and the influence of C1 located close to NH3 in the [NH3(CH2)6NH3] cation near T C are determined to be large, which implies that the structural change of CuCl4 linked to N-H⋯Cl is large. The 1H spin-lattice relaxation time (T 1ρ) in NH3 is shorter than that of CH2, and the 13C T 1ρ values for C1 close to NH3 are shorter than those of C2 and C3 due to the influence of the paramagnetic Cu2+ ion in square planar geometry CuCl4. The structural mechanism for the phase transition was the change in the N-H⋯Cl hydrogen bond and was associated with the structural dynamics of the CuCl4 anion.

Characterization on Lead-Free Hybrid Perovskite [NH3(CH2)5NH3]CuCl4: Thermodynamic Properties and Molecular Dynamics.

It is essential to develop novel zero- and two-dimensional hybrid perovskites to facilitate the development of eco-friendly solar cells. In this study, we investigated the structure and dynamics of [NH3(CH2)5NH3]CuCl4 via various characterization techniques. Nuclear magnetic resonance (NMR) results indicated that the crystallographic environments of 1H in NH3 and 13C on C3, located close to NH3 at both ends of the cation, were changed, indicating a large structural change of CuCl6 connected to N-H···Cl. The thermal properties and structural dynamics of the [NH3(CH2)nNH3] cation in [NH3(CH2)nNH3]CuCl4 (n = 2, 3, 4, and 5) crystals were compared using thermogravimetric analysis (TGA) and NMR results for the methylene chain. The 1H and 13C spin-lattice relaxation times (T1ρ) exhibited similar trends upon the variation of the methylene chain length, with n = 2 exhibiting shorter T1ρ values than n = 3, 4, and 5. The difference in T1ρ values was related to the length of the cation, and the shorter chain length (n = 2) exhibited a shorter T1ρ owing to the one closest to the paramagnetic Cu2+ ions.

Advances in physicochemical characterization of lead-free hybrid perovskite [NH3(CH2)3NH3]CuBr4 crystals.

To support the development of eco-friendly hybrid perovskite solar cells, structural, thermal, and physical properties of the lead-free hybrid perovskite [NH3(CH2)3NH3]CuBr4 were investigated using X-ray diffraction (XRD), differential scanning calorimetry, thermogravimetric analysis, and nuclear magnetic resonance spectroscopy. The crystal structure confirmed by XRD was monoclinic, and thermodynamic stability was observed at approximately 500 K without any phase transition. The large changes in the 1H chemical shifts of NH3 and those in C2 close to N are affected by N-H∙∙∙Br hydrogen bonds because the structural geometry of CuBr4 changed significantly. The 1H and 13C spin-lattice relaxation times (T1ρ) showed very similar molecular motions according to the Bloembergen-Purcell-Pound theory at low temperatures; however, the 1H T1ρ values representing energy transfer were about 10 times lesser than those of 13C T1ρ. Finally, the 1H and 13C T1ρ values of [NH3(CH2)3NH3]MeBr4 (Me = Cu, Zn, and Cd) were compared with those reported previously. 1H T1ρ was affected by the paramagnetic ion of the anion, while 13C T1ρ was affected by the MeBr4 structure of the anion; 13C T1ρ values in Me = Cu and Cd with the octahedral MeBr6 structure had longer values than those in Me = Zn with the tetrahedral MeBr4 structure. We believe that these detailed insights on the physical properties will play a crucial role in the development of eco-friendly hybrid perovskite solar cells.

Study on structural geometry and dynamic property of [NH3(CH2)5NH3]CdCl4 crystal at phases I, II, and III.

Organic-inorganic hybrid perovskites can potentially be used in electrochemical devices, such as batteries and fuel cells. In this study, the structure and phase transition temperatures of the organic-inorganic material [NH3(CH2)5NH3]CdCl4 crystal were confirmed by X-ray diffraction and differential scanning calorimetry. From the nuclear magnetic resonance results, the crystallographic configurations of 1H, 13C, and 14N in the cation changed at temperatures close to TC1 (336 K), whereas that of 113Cd in the anion shows significant changes at temperatures close to TC1 and TC2 (417 K). The activation energy, Ea, values for 1H and 13C obtained from the spin-lattice relaxation time, T1ρ, below and above TC1 were evaluated, where the Ea value for 13C was more flexible at low temperatures than at high temperatures. In addition, the effect on molecular motion was effective at high temperatures. The phase transition at 336 K was associated with the change in the N-H···Cl bond due to the change in the coordination geometry of Cl around Cd in the CdCl6 anion. On the other hand, the phase transition at 417 K was related to the ferroelastic phase transition attributed to the twin domains.

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

Hybrid perovskites have potential applications in several electrochemical devices such as supercapacitors, batteries, and fuel cells. Here, the thermal stabilities as a function of the length n of the CH2 groups in [NH3(CH2) n NH3]CdCl4 (n = 2, 3, and 4) crystals were considered by TGA and DTA. The structural characteristics and molecular dynamics were studied by MAS and static NMR experiments. A comparison of spin-lattice relaxation times indicated that the organic cation containing 1H and 13C was significantly more flexible than the inorganic anion containing 113Cd. The flexibility of 1H increased with an increase in the length of CH2 in the carbon chain, resulting in a decrease in the activation energy (E a) of 1H. The E a of 13C at n = 3 and 4 was more flexible at high temperatures than at low temperatures. In contrast, the E a of 13C at n = 2 was more flexible at low temperatures. These results provide insight into the thermal stability and molecular dynamics of these crystals as a function of the length n of CH2 groups in the carbon chain and are expected to facilitate applications.

A prospect of cost-effective handling and transportation of graphene oxides: folding and redispersion of graphene oxide microsheets.

Controlling the assembly of 2D materials such as graphene oxides (GO) has a significant impact on their properties and performance. One of the critical issues on the processing and handling of GO is that they need to be in dilution solution (0.5 to 2.5 wt%) to maintain their high degree of exfoliation and dispersion. As a result, the shipment of GO in large quantity involves a huge volume of solvent (water) and thus the transportation costs for large sales volume would become extremely high. Through cross-sectional scanning electron microscopy and polarized optical microscopy together with x-ray diffraction and small-angle x-ray scattering studies, we demonstrated that the assembly and structure of GO microsheets can be preserved without restacking, when assembled GO via water-based wet spinning are re-dispersed into solution. A couple of alkyl ammonium bromides, CTAB and TBAB, as well as NaOH, were examined as coagulants and the resulting fibers were redispersed in an aqueous solution. The redispersed solution of fibers that were wet-spun into the commonly used CTAB and TBAB coagulation baths, maintained their physico-chemical properties (similar to the original GO dispersion) however, did not reveal preservation of liquid crystallinity. Meanwhile, the redispersed fibers that were initially spun into NaOH coagulation bath were able to maintain their liquid crystallinity if the lateral size of the GO sheets was large. Based on these findings, a cost-effective solid handling approach is devised which involves (i) processing GO microsheets in solution into folded layers in solid-state, (ii) transporting assembled GO to the customers, and (iii) redispersion of folded GO into a solution for their use. The proposed solid handling of GO followed by redispersion into solution can greatly reduce the transportation costs of graphene oxide materials by reducing the transportation volume by more than 90%.

Effect of Methylene Chain Length on the Thermodynamic Properties, Ferroelastic Properties, and Molecular Dynamics of the Perovskite-type Layer Crystal [NH3(CH2) n NH3]MnCl4 (n = 2, 3, and 4).

The structures and phase transitions of [NH3(CH2) n NH3]MnCl4 (n = 2, 3, and 4) crystals were confirmed through X-ray diffraction and differential scanning calorimetry (DSC) experiments. Thermodynamic properties, ferroelastic properties, and molecular dynamics of three crystals were studied as a function of the number (n) of CH2 groups in the alkylene chains. The loss in molecular weight due to a decrease in n marked the onset of the partial thermal decomposition. The thermal decomposition temperature, T d, increased with increasing length of the CH2 chain. While the ferroelastic twin domain walls for n = 2 and 4 were in the same direction at all temperatures, the domain walls for n = 3 were rotated by 45°, and the direction of extinction in phase II was rotated by 45° with respect to phases I and III. The 1H and 13C MAS NMR spectra of the three crystals were recorded as a function of temperature. With increasing length of the CH2 chain, the 1H spin relaxation time decreased, indicating that molecular motions were activated. These results provide insights into the thermodynamic properties and structural dynamics of the [NH3(CH2) n NH3]MnCl4 crystals and are expected to facilitate their potential applications.