Theoretical spectroscopy of a NIR-absorbing benziphthalocyanine dye
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Benziphthalocyanines are (Yanai et al. in Chem Phys Lett 393:51–57, 2004) phthalocyanines in which one isoindoline unit has been replaced by a phenyl ring. In this study, we focus on a macrocycle of this family recently synthesized by Uchiyama and co-workers (Toriumi et al. Angew Chem Int Ed 53:7814–7818, 2014), and composed of three indoline units (substituted with 2,6-diisopropylphenyl-oxy groups) and one resorcinol unit. We aim at characterizing the possible tautomers to evaluate whether this compound might exist as a mixture of several forms or not. To reach our goals, we use state-of-the-art ab initio theories, i.e., Time-Dependent Density Functional Theory coupled with a refined solvation model (the Polarizable Continuum Model) as well as post-Hartree Fock approaches. We first investigate the stability, the structure and the aromaticity of the possible tautomers before analyzing their spectroscopic signatures. Using an approach going beyond the vertical approximation, we compare experimental and theoretical 0–0 energies and band shapes. This study allows us to point out the dominant presence of the quinoidal form as well as to unravel the vibronic contributions responsible for the specific shape of the optical spectrum.
KeywordsTD-DFT CC2 Macrocycles Optical spectra
The authors are indebted to Dr. C. A. Guido for his help with the FCHT spectra. P. M. V and D. J. thank the ANR for support in the framework of the GEDEMI Grant. C. A. and D. J. received support from the ANR in the framework of the EMA Grant. This research used resources of (i) the GENCI-CINES/IDRIS; (ii) CCIPL (Centre de Calcul Intensif des Pays de Loire); (iii) a local Troy cluster and (iv) HPC resources from ArronaxPlus (Grant ANR-11-EQPX-0004 funded by the French National Agency for Research).
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