Structural geometry and molecular dynamics of hybrid organic-inorganic [NH 3 (CH 2 ) 6 NH 3 ]CdCl 4 crystals close to phase transition temperatures

Organic-inorganic hybrid perovskites are highly promising for application in various electrochemical de-vices, such as batteries and fuel cells. The physical properties of crystals of the organic-inorganic hy-brid perovskite [NH3(CH2)6NH3]CdCl4 are important for their future application. Therefore, these crystals were grown and their phase transition temperatures TC1 = 337 K and TC2 = 472 K were determined us-ing powder X-ray diffraction and differential scanning calorimetry. We observed that the crystallographic surroundings of 1H and 13C in the cation near TC1 did not show significant changes, whereas those of 113Cd in the anion changed significantly. The change in the coordination geometry of C1 around Cd near TC1 changed the N-HmiddotmiddotmiddotCl bond by connecting with the 1H of NH3. The nuclear magnetic resonance spin-lattice relaxation time T1 rho suggested that the 1H energy transfer processes in phases III and II were eas-ier, whereas the 13C energy transfer processes were easier in phase III than in phase II. The results of the current study for [NH3(CH2)nNH3]CdCl4 (n = 6) were compared with those for n = 2, 3, 4, and 5 obtained from previous studies. The features of the length of CH2 and even-odd number of carbons in the diammonium chain are expected to facilitate potential applications in the future.(c) 2023 Elsevier B.V. All rights reserved.

Automated summary

Organic-inorganic hybrid perovskites show great potential for use in various electrochemical devices. In this study, [NH3(CH2)6NH3]CdCl4 crystals were grown and their phase transition temperatures were determined. The crystallographic structure of the cation near TC1 remained unchanged, while that of the anion showed significant changes around 113Cd.