Comparative electronic structures and UV-vis spectra of tribenzosubporphyrin, tribenzomonoazasubporphyrin, tribenzodiazasubporphyrin, and subphthalocyanine: Insight from DFT and TDDFT calculations

Yunling Gao, Pavlo Solntsev, Victor N. Nemykin

Research output: Contribution to journalArticle

15 Scopus citations

Abstract

Electronic structures, geometries, and vertical excitation energies of chloroboron subphthalocyanine, tribenzodiazasubporphyrin, tribenzomonoazasubporphyrin, and tribenzosubporphyrin were calculated using density functional theory (DFT) and time-dependent (TD) DFT coupled with polarized continuum model (PCM) approach. Molecular geometries calculated at the BP86/6-311G(d) level reveal bowl-shape, trigonal prismatic conformations for all compounds with a variable bowl-depth that depends on the number of meso-nitrogen atoms in corresponding molecule. TDDFT-PCM calculations predict that the Q-band should undergo gradual high-energy shift, while the B-band should undergo low-energy shift upon stepwise substitution of the meso-nitrogen atoms in subphthalocyanine toward tribenzosubporphyrin. The TDDFT-PCM predicted trend was rationalized on the basis of electronic structures of target macrocycles. When comparison between theory and experiment is available, TDDFT-PCM calculations are in qualitative and quantitative agreement with experimental data.

Original languageEnglish (US)
Pages (from-to)369-374
Number of pages6
JournalJournal of Molecular Graphics and Modelling
Volume38
DOIs
StatePublished - Sep 1 2012

Keywords

  • Electronic structure
  • Subphthalocyanine
  • Subporphyrin
  • TDDFT
  • Vertical excitation energies

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