Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts

• Published in: Molecules (Basel, Switzerland) Vol. 29; no. 1; p. 78
• Main Authors: Samsonova, Anna Yu, Mikheleva, Alena Yu, Bulanin, Kirill M, Selivanov, Nikita I, Mazur, Anton S, Tolstoy, Peter M, Stoumpos, Constantinos C, Kapitonov, Yury V
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 22-12-2023; MDPI
• Subjects: Asymmetry; Carbon; Crystal structure; halide perovskites; Hydrocarbons; IR absorption; molecular vibrations; Neutrons; NMR; Nuclear magnetic resonance; Perovskite; Phase transitions; Raman scattering; solid-state NMR; Spectrum analysis; Symmetry; Temperature; molecular vibrations; IR absorption; solid-state NMR; halide perovskites; Raman scattering
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules29010078

We investigate vibrations of the pyridinium cation PyH
= C
H
NH
in one-dimensional lead halide perovskites PyPbX
and pyridinium halide salts PyHX (X
= I
, Br
), combining infrared absorption and Raman scattering methods at room temperature. Internal vibrations of the cation were assigned based on density functional theory modeling. Some of the vibrational bands are sensitive to perovskite or the salt environment in the solid state, while halide substitution has only a minor effect on them. These findings have been confirmed by
H,
C and
Pb solid-state nuclear magnetic resonance (NMR) experiments. Narrower vibrational bands in perovskites indicate less disorder in these materials. The splitting of NH-group vibrational bands in perovskites can be rationalized the presence of nonequivalent crystal sites for cations or by more exotic phenomena such as quantum tunneling transition between two molecular orientations. We have shown how organic cations in hybrid organic-inorganic crystals could be used as spectators of the crystalline environment that affects their internal vibrations.