Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts
We investigate vibrations of the pyridinium cation PyH<sup>+</sup> = C<sub>5</sub>H<sub>5</sub>NH<sup>+</sup> in one-dimensional lead halide perovskites PyPbX<sub>3</sub> and pyridinium halide salts PyHX (X<sup>−</sup> = I<su...
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MDPI AG
2023-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/29/1/78 |
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| author | Anna Yu. Samsonova Alena Yu. Mikheleva Kirill M. Bulanin Nikita I. Selivanov Anton S. Mazur Peter M. Tolstoy Constantinos C. Stoumpos Yury V. Kapitonov |
| author_facet | Anna Yu. Samsonova Alena Yu. Mikheleva Kirill M. Bulanin Nikita I. Selivanov Anton S. Mazur Peter M. Tolstoy Constantinos C. Stoumpos Yury V. Kapitonov |
| author_sort | Anna Yu. Samsonova |
| collection | DOAJ |
| description | We investigate vibrations of the pyridinium cation PyH<sup>+</sup> = C<sub>5</sub>H<sub>5</sub>NH<sup>+</sup> in one-dimensional lead halide perovskites PyPbX<sub>3</sub> and pyridinium halide salts PyHX (X<sup>−</sup> = I<sup>−</sup>, Br<sup>−</sup>), 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 <sup>1</sup>H, <sup>13</sup>C and <sup>207</sup>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. |
| first_indexed | 2024-03-08T15:01:24Z |
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| id | doaj.art-79ae1d266250459594532e31f4ff76dc |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-08T15:01:24Z |
| publishDate | 2023-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-79ae1d266250459594532e31f4ff76dc2024-01-10T15:04:05ZengMDPI AGMolecules1420-30492023-12-012917810.3390/molecules29010078Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide SaltsAnna Yu. Samsonova0Alena Yu. Mikheleva1Kirill M. Bulanin2Nikita I. Selivanov3Anton S. Mazur4Peter M. Tolstoy5Constantinos C. Stoumpos6Yury V. Kapitonov7Photonics of Crystals Laboratory, Saint Petersburg State University, Ulyanovskaya d.1, 198504 St. Petersburg, RussiaPhotonics of Crystals Laboratory, Saint Petersburg State University, Ulyanovskaya d.1, 198504 St. Petersburg, RussiaPhotonics of Crystals Laboratory, Saint Petersburg State University, Ulyanovskaya d.1, 198504 St. Petersburg, RussiaPhotonics of Crystals Laboratory, Saint Petersburg State University, Ulyanovskaya d.1, 198504 St. Petersburg, RussiaMagnetic Resonance Research Center, Saint Petersburg State University, Universitetskiy pr. 26, 198504 St. Petersburg, RussiaInstitute of Chemistry, Saint Petersburg State University, Universitetskiy pr. 26, 198504 St. Petersburg, RussiaPhotonics of Crystals Laboratory, Saint Petersburg State University, Ulyanovskaya d.1, 198504 St. Petersburg, RussiaPhotonics of Crystals Laboratory, Saint Petersburg State University, Ulyanovskaya d.1, 198504 St. Petersburg, RussiaWe investigate vibrations of the pyridinium cation PyH<sup>+</sup> = C<sub>5</sub>H<sub>5</sub>NH<sup>+</sup> in one-dimensional lead halide perovskites PyPbX<sub>3</sub> and pyridinium halide salts PyHX (X<sup>−</sup> = I<sup>−</sup>, Br<sup>−</sup>), 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 <sup>1</sup>H, <sup>13</sup>C and <sup>207</sup>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.https://www.mdpi.com/1420-3049/29/1/78halide perovskitesRaman scatteringIR absorptionsolid-state NMRmolecular vibrations |
| spellingShingle | Anna Yu. Samsonova Alena Yu. Mikheleva Kirill M. Bulanin Nikita I. Selivanov Anton S. Mazur Peter M. Tolstoy Constantinos C. Stoumpos Yury V. Kapitonov Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts Molecules halide perovskites Raman scattering IR absorption solid-state NMR molecular vibrations |
| title | Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts |
| title_full | Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts |
| title_fullStr | Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts |
| title_full_unstemmed | Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts |
| title_short | Internal Vibrations of Pyridinium Cation in One-Dimensional Halide Perovskites and the Corresponding Halide Salts |
| title_sort | internal vibrations of pyridinium cation in one dimensional halide perovskites and the corresponding halide salts |
| topic | halide perovskites Raman scattering IR absorption solid-state NMR molecular vibrations |
| url | https://www.mdpi.com/1420-3049/29/1/78 |
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