Origin of the Solvatochromism in Organic Fluorophores with Flexible Side Chains: A Case Study of Flugi-2
| Autor: | Marcus Elstner, Sebastian Höfener, Franziska E. Wolff, Tomasz Adam Wesolowski |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
010304 chemical physics
Proton Hydrogen bond Physics::Medical Physics Solvatochromism Hydrogen atom Decane 010402 general chemistry 01 natural sciences 0104 chemical sciences chemistry.chemical_compound Molecular dynamics chemistry Chemical physics ddc:540 0103 physical sciences Potential energy surface Molecule Physical and Theoretical Chemistry |
| Zdroj: | Journal of Physical Chemistry. A, Vol. 123, No 21 (2019) pp. 4581-4587 |
| ISSN: | 1520-5215 1089-5639 |
| DOI: | 10.1021/acs.jpca.9b02474 |
| Popis: | The emission band for Flugi-2 solvated in dimethyl sulfoxide (DMSO) is obtained from the combined quantum-classical simulations in which the quantum mechanics/molecular mechanics excitation energies are evaluated at the equilibrated segment of the classical molecular dynamics trajectory on the lowest-excited-state potential energy surface. The classical force-field parameters were obtained and validated specifically for the purpose of the present work. The calculated gas-phase to DMSO solvatochromic shift amounts to -0.21 eV, which is in line with the experimentally determined difference between the maxima of the emission bands for Flugi-2 in decane and in DMSO (-0.26 eV). The used model describes rather well the effect of DMSO on the broadening of the emission band. The solvatochromic shift in DMSO originates from two competing effects. The structural deformation of Flugi-2 due to the interaction with DMSO, which results in a positive contribution, and the negative contribution of a larger magnitude due to favorable specific interactions with the solvent. The latter is dominated by a single hydrogen bond between the oxygen atom of a DMSO molecule and the N3 hydrogen atom of the Flugi-2 molecule in which the proton of N3 acts as the donor. |
| Databáze: | OpenAIRE |
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