| Autor: |
Zobel JP; Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna Währingerstr. 19 1090 Vienna Austria patrick.zobel@univie.ac.at leticia.gonzalez@univie.ac.at., Knoll T; Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna Währingerstr. 19 1090 Vienna Austria patrick.zobel@univie.ac.at leticia.gonzalez@univie.ac.at., González L; Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna Währingerstr. 19 1090 Vienna Austria patrick.zobel@univie.ac.at leticia.gonzalez@univie.ac.at.; Vienna Research Platform on Accelerating Photoreaction Discovery, University of Vienna Währingerstr. 19 1090 Vienna Austria. |
| Jazyk: |
angličtina |
| Zdroj: |
Chemical science [Chem Sci] 2021 May 26; Vol. 12 (32), pp. 10791-10801. Date of Electronic Publication: 2021 May 26 (Print Publication: 2021). |
| DOI: |
10.1039/d1sc02149d |
| Abstrakt: |
We report the non-adiabatic dynamics of V III Cl 3 (ddpd), a complex based on the Earth-abundant first-row transition metal vanadium with a d 2 electronic configuration which is able to emit phosphorescence in solution in the near-infrared spectral region. Trajectory surface-hopping dynamics based on linear vibronic coupling potentials obtained with CASSCF provide molecular-level insights into the intersystem crossing from triplet to singlet metal-centered states. While the majority of the singlet population undergoes back-intersystem crossing to the triplet manifold, 1-2% remains stable during the 10 ps simulation time, enabling the phosphorescence described in Dorn et al. Chem. Sci. , 2021, DOI: 10.1039/D1SC02137K. Competing with intersystem crossing, two different relaxation channels via internal conversion through the triplet manifold occur. The nuclear motion that drives the dynamics through the different electronic states corresponds mainly to the increase of all metal-ligand bond distances as well as the decrease of the angles of trans-coordinated ligand atoms. Both motions lead to a decrease in the ligand-field splitting, which stabilizes the interconfigurational excited states populated during the dynamics. Analysis of the electronic character of the states reveals that increasing and stabilizing the singlet population, which in turn can result in enhanced phosphorescence, could be accomplished by further increasing the ligand-field strength.
Competing Interests: There are no conflicts to declare.
(This journal is © The Royal Society of Chemistry.) |
| Databáze: |
MEDLINE |
| Externí odkaz: |
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