Substituent effects on the photophysical properties of amino-aurone-derivatives |
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Authors: | Karina Muñoz-Becerra Nery Villegas-Escobar César Zúñiga-Loyola Diego Cortés-Arriagada |
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Affiliation: | 1. Laboratorio de Química Teórica Computacional (QTC), Facultad de Química y de Farmacia and Centro Energía UC, Pontificia Universidad Católica de Chile, Santiago, Chile;2. Centro de Investigación de Nanotecnología y Materiales Avanzados, CIEN-UC. Pontificia Universidad Católica de Chile, Santiago, Chile https://orcid.org/0000-0001-9882-6342;3. Laboratorio de Química Teórica Computacional (QTC), Facultad de Química y de Farmacia and Centro Energía UC, Pontificia Universidad Católica de Chile, Santiago, Chile https://orcid.org/0000-0002-6370-617X;4. Centro de Investigación de Nanotecnología y Materiales Avanzados, CIEN-UC. Pontificia Universidad Católica de Chile, Santiago, Chile https://orcid.org/0000-0002-0894-3383;5. Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, Santiago, Chile https://orcid.org/0000-0002-6709-1723 |
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Abstract: | ABSTRACTAurones are potential candidates to be employed as fluorescent probes or as pharmacophores for biological applications. This work describes a density functional theory (DFT) and time-dependent -DFT study at the PBE0/6-31?+?G(d) level of theory to analyse the structural, electronic and photophysical properties of a series of new proposed 4′-amine-aurone derivatives in its E and Z isomeric conformations. The maximum absorption wavelength of the proposed aurones appears in the range 390???514?nm, while the most allowed emission pathways were computed in the range 493–530?nm. The bathochromic shift of these compounds with respect to the non-substituted aurone is modulated by the acceptor strength of the added 4-substituents, in addition to the ability of the substituents to localise the frontier molecular orbitals over the acceptor benzofuranone moiety without losing the tricyclic planarity, which favours the push–pull nature of these molecules. The influence of the 4-substituent is also evidenced in the Stokes shifts for the whole series; as the electron-withdrawing character of the 4-substituents enhances, higher is the polarisation of the structure resulting in higher Stokes shifts. As a result, -CF3 and -NO2 substituents were responsible of larger Stokes shifts, then compounds containing these substituents are proposed as potential fluorescence probes for useful applications in biological systems. |
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Keywords: | Aurones DFT calculations chromophores organic dyes fluorescence probes |
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