title: Comparative electronic structures and UV-vis spectra of tribenzosubporphyrin, tribenzomonoazasubporphyrin, tribenzodiazasubporphyrin, and subphthalocyanine: insight from DFT and TDDFT calculations.
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.
authors.affiliation: Department of Chemistry and Biochemistry, University of Minnesota-Duluth, Duluth, MN 55812, USA.
authors.forename: Yunling
authors.initials: Y
authors.lastname: Gao
authors.forename: Pavlo V
authors.initials: PV
authors.lastname: Solntsev
authors.forename: Victor N
authors.initials: VN
authors.lastname: Nemykin
mesh_terms: D001372:Aza Compounds / Q000737:chemistry*; D001895:Boron; D056831:Coordination Complexes / Q000737:chemistry*; D004583:Electrons; D054833:Isoindoles / Q000737:chemistry*; D008968:Molecular Conformation; D011166:Porphyrins / Q000737:chemistry*; D011789:Quantum Theory; D012997:Solvents; D013056:Spectrophotometry, Ultraviolet
chemical_list: D001372:Aza Compounds; D056831:Coordination Complexes; D054833:Isoindoles; D011166:Porphyrins; D012997:Solvents; D001895:Boron