Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR
At low temperature, methyl groups act as hindered quantum rotors exhibiting rotational quantum tunneling, which is highly sensitive to a local methyl group environment. Recently, we observed this effect using pulsed electron paramagnetic resonance (EPR) in two dimethylammonium-containing hybrid pero...
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MDPI AG
2023-01-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/3/979 |
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| author | Gediminas Usevičius Andrea Eggeling Ignas Pocius Vidmantas Kalendra Daniel Klose Mirosław Mączka Andreas Pöppl Jūras Banys Gunnar Jeschke Mantas Šimėnas |
| author_facet | Gediminas Usevičius Andrea Eggeling Ignas Pocius Vidmantas Kalendra Daniel Klose Mirosław Mączka Andreas Pöppl Jūras Banys Gunnar Jeschke Mantas Šimėnas |
| author_sort | Gediminas Usevičius |
| collection | DOAJ |
| description | At low temperature, methyl groups act as hindered quantum rotors exhibiting rotational quantum tunneling, which is highly sensitive to a local methyl group environment. Recently, we observed this effect using pulsed electron paramagnetic resonance (EPR) in two dimethylammonium-containing hybrid perovskites doped with paramagnetic Mn<sup>2+</sup> ions. Here, we investigate the feasibility of using an alternative fast-relaxing Co<sup>2+</sup> paramagnetic center to study the methyl group tunneling, and, as a model compound, we use dimethylammonium zinc formate [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] hybrid perovskite. Our multifrequency (X-, Q- and W-band) EPR experiments reveal a high-spin state of the incorporated Co<sup>2+</sup> center, which exhibits fast spin-lattice relaxation and electron spin decoherence. Our pulsed EPR experiments reveal magnetic field independent electron spin echo envelope modulation (ESEEM) signals, which are assigned to the methyl group tunneling. We use density operator simulations to extract the tunnel frequency of 1.84 MHz from the experimental data, which is then used to calculate the rotational barrier of the methyl groups. We compare our results with the previously reported Mn<sup>2+</sup> case showing that our approach can detect very small changes in the local methyl group environment in hybrid perovskites and related materials. |
| first_indexed | 2024-03-11T09:34:38Z |
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| language | English |
| last_indexed | 2024-03-11T09:34:38Z |
| publishDate | 2023-01-01 |
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| record_format | Article |
| series | Molecules |
| spelling | doaj.art-ae33fe9d47f94db7b5de8b341a4bcd752023-11-16T17:25:51ZengMDPI AGMolecules1420-30492023-01-0128397910.3390/molecules28030979Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPRGediminas Usevičius0Andrea Eggeling1Ignas Pocius2Vidmantas Kalendra3Daniel Klose4Mirosław Mączka5Andreas Pöppl6Jūras Banys7Gunnar Jeschke8Mantas Šimėnas9Faculty of Physics, Vilnius University, Sauletekio 3, 10257 Vilnius, LithuaniaDepartment of Physical Chemistry, ETH-Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, SwitzerlandFaculty of Physics, Vilnius University, Sauletekio 3, 10257 Vilnius, LithuaniaFaculty of Physics, Vilnius University, Sauletekio 3, 10257 Vilnius, LithuaniaDepartment of Physical Chemistry, ETH-Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, SwitzerlandInstitute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wroclaw, PolandFelix Bloch Institute for Solid State Physics, Leipzig University, 04103 Leipzig, GermanyFaculty of Physics, Vilnius University, Sauletekio 3, 10257 Vilnius, LithuaniaDepartment of Physical Chemistry, ETH-Zürich, Vladimir-Prelog-Weg 2, 8093 Zürich, SwitzerlandFaculty of Physics, Vilnius University, Sauletekio 3, 10257 Vilnius, LithuaniaAt low temperature, methyl groups act as hindered quantum rotors exhibiting rotational quantum tunneling, which is highly sensitive to a local methyl group environment. Recently, we observed this effect using pulsed electron paramagnetic resonance (EPR) in two dimethylammonium-containing hybrid perovskites doped with paramagnetic Mn<sup>2+</sup> ions. Here, we investigate the feasibility of using an alternative fast-relaxing Co<sup>2+</sup> paramagnetic center to study the methyl group tunneling, and, as a model compound, we use dimethylammonium zinc formate [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] hybrid perovskite. Our multifrequency (X-, Q- and W-band) EPR experiments reveal a high-spin state of the incorporated Co<sup>2+</sup> center, which exhibits fast spin-lattice relaxation and electron spin decoherence. Our pulsed EPR experiments reveal magnetic field independent electron spin echo envelope modulation (ESEEM) signals, which are assigned to the methyl group tunneling. We use density operator simulations to extract the tunnel frequency of 1.84 MHz from the experimental data, which is then used to calculate the rotational barrier of the methyl groups. We compare our results with the previously reported Mn<sup>2+</sup> case showing that our approach can detect very small changes in the local methyl group environment in hybrid perovskites and related materials.https://www.mdpi.com/1420-3049/28/3/979methyl group tunnelinghybrid perovskiteEPRESEEM |
| spellingShingle | Gediminas Usevičius Andrea Eggeling Ignas Pocius Vidmantas Kalendra Daniel Klose Mirosław Mączka Andreas Pöppl Jūras Banys Gunnar Jeschke Mantas Šimėnas Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR Molecules methyl group tunneling hybrid perovskite EPR ESEEM |
| title | Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR |
| title_full | Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR |
| title_fullStr | Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR |
| title_full_unstemmed | Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR |
| title_short | Probing Methyl Group Tunneling in [(CH<sub>3</sub>)<sub>2</sub>NH<sub>2</sub>][Zn(HCOO)<sub>3</sub>] Hybrid Perovskite Using Co<sup>2+</sup> EPR |
| title_sort | probing methyl group tunneling in ch sub 3 sub sub 2 sub nh sub 2 sub zn hcoo sub 3 sub hybrid perovskite using co sup 2 sup epr |
| topic | methyl group tunneling hybrid perovskite EPR ESEEM |
| url | https://www.mdpi.com/1420-3049/28/3/979 |
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