CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex
Ruthenium nitrosyl complexes are fascinating photoactive compounds showing complex photoreactivity, such as N→O linkage photoisomerism and NO photorelease. This dual photochemical behavior has been the subject of many experimental studies in order to optimize these systems for applications as photos...
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| Format: | Article |
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MDPI AG
2020-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/25/11/2613 |
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| author | Francesco Talotta Leticia González Martial Boggio-Pasqua |
| author_facet | Francesco Talotta Leticia González Martial Boggio-Pasqua |
| author_sort | Francesco Talotta |
| collection | DOAJ |
| description | Ruthenium nitrosyl complexes are fascinating photoactive compounds showing complex photoreactivity, such as N→O linkage photoisomerism and NO photorelease. This dual photochemical behavior has been the subject of many experimental studies in order to optimize these systems for applications as photoswitches or therapeutic agents for NO delivery. However, despite recent experimental and computational studies along this line, the underlying photochemical mechanisms still need to be elucidated for a more efficient design of these systems. Here, we present a theoretical contribution based on the calculations of excited-state potential energy profiles for NO dissociation in the prototype <i>trans</i>-[RuCl(NO)(py)<sub>4</sub>]<sup>2+</sup> complex at the complete active space second-order perturbation theory (CASPT2). The results point to a sequential two-step photon absorption photorelease mechanism coupled to partial photoisomerization to a side-on intermediate, in agreement with previous density functional theory calculations. |
| first_indexed | 2024-03-10T19:22:36Z |
| format | Article |
| id | doaj.art-395e3f86f1dd4fa48cc739eea1d8f27d |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T19:22:36Z |
| publishDate | 2020-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-395e3f86f1dd4fa48cc739eea1d8f27d2023-11-20T02:49:36ZengMDPI AGMolecules1420-30492020-06-012511261310.3390/molecules25112613CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl ComplexFrancesco Talotta0Leticia González1Martial Boggio-Pasqua2Institut de Chimie et Physique, UMR 8000 CNRS/Université Paris-Saclay, 91405 Orsay, FranceInstitut für Theoretische Chemie, Fakultät für Chemie, Universität Wien, Währinger Strasse 17, 1090 Vienna, AustriaLaboratoire de Chimie et Physique Quantiques, IRSAMC, CNRS/Université Toulouse 3, 118 route de Narbonne, 31062 Toulouse, FranceRuthenium nitrosyl complexes are fascinating photoactive compounds showing complex photoreactivity, such as N→O linkage photoisomerism and NO photorelease. This dual photochemical behavior has been the subject of many experimental studies in order to optimize these systems for applications as photoswitches or therapeutic agents for NO delivery. However, despite recent experimental and computational studies along this line, the underlying photochemical mechanisms still need to be elucidated for a more efficient design of these systems. Here, we present a theoretical contribution based on the calculations of excited-state potential energy profiles for NO dissociation in the prototype <i>trans</i>-[RuCl(NO)(py)<sub>4</sub>]<sup>2+</sup> complex at the complete active space second-order perturbation theory (CASPT2). The results point to a sequential two-step photon absorption photorelease mechanism coupled to partial photoisomerization to a side-on intermediate, in agreement with previous density functional theory calculations.https://www.mdpi.com/1420-3049/25/11/2613photoreleasephotoisomerizationphotochromismcomputational photochemistryab initio calculations |
| spellingShingle | Francesco Talotta Leticia González Martial Boggio-Pasqua CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex Molecules photorelease photoisomerization photochromism computational photochemistry ab initio calculations |
| title | CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex |
| title_full | CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex |
| title_fullStr | CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex |
| title_full_unstemmed | CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex |
| title_short | CASPT2 Potential Energy Curves for NO Dissociation in a Ruthenium Nitrosyl Complex |
| title_sort | caspt2 potential energy curves for no dissociation in a ruthenium nitrosyl complex |
| topic | photorelease photoisomerization photochromism computational photochemistry ab initio calculations |
| url | https://www.mdpi.com/1420-3049/25/11/2613 |
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