Azarias, C.; Ponce-Vargas, M.; Fleurat-Lessard, P.; Romieu, A.; Le Guennic, B.; Richard, J. A.; Jacquemin, D., Rationalisation of the optical signatures of nor-dihydroxanthene-hemicyanine fused near-infrared fluorophores by first-principle tools. Physical Chemistry Chemical Physics 2018, 20 (17), 12120-12128.
Abstract:
Using a computational approach combining the Time-Dependent Density Functional Theory (TD-DFT) and the second-order Coupled Cluster (CC2) approaches, we investigate the spectral properties of a large panel of nor-dihydroxanthene (DHX)-hemicyanine fused dyes. First we compare the theoretical and experimental 0–0 energies for a set of 14 known synthetic compounds and show that a remarkable agreement between theory and experiment is obtained when a suitable environmental model is selected. In addition, we obtain vibrationally-resolved spectra for several compounds and theory also accurately reproduces the experimental band shapes. We show that the electronic transitions in nor-DHX-based fluorophores are associated with small variations of the dipole moments but large oscillator strengths. Using various chemical strategies, we design a series of compounds with red-shifted 0–0 energies.
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Funding Info:
This work was supported by ANR for the EMA grant, the PHC Merlion program (grant 5.04.15), Institut Universitaire de France (IUF) and the Burgundy region (‘‘FABER’’ programme, PARI Action 6, SSTIC 6 ‘‘Imagerie, instrumentation, chimie et applications biome´dicales’’), and ICES, A*STAR (Singapore).