title: Systematic investigation of phthalocyanines, naphthalocyanines, and their aza-analogues. Effect of the isosteric aza-replacement in the core.
abstract: A series of zinc complexes of phthalocyanine, naphthalocyanine and their aza-analogues with alkylsulfanyl substituents was synthesized and characterized by UV-vis and MCD spectroscopy, and their redox properties were investigated using CV, DPV, and SWV approaches as well as spectroelectrochemical methods. Aggregation, photostability, singlet oxygen production, and fluorescence quantum yields of the target complexes were studied as a function of the stepwise substitution of the aromatic C-H fragments by nitrogen atoms. The electronic structure and vertical excitation energies of the target compounds were probed by DFT-PCM and TDDFT-PCM approaches. Introduction of additional nitrogens into the structure leads to a hypsochromic shift of the Q-band and makes the macrocycle strongly electron deficient and more photostable. The impact on the photophysics is limited. The relationships between the type of macrocycle and the studied properties were defined.
authors.affiliation: Department of Biophysics and Physical Chemistry, Faculty of Pharmacy in Hradec Kralove, Charles University in Prague, Heyrovskeho 1203, 50005, Hradec Kralove, Czech Republic. veronika.novakova@faf.cuni.cz.
authors.forename: Veronika
authors.initials: V
authors.lastname: Novakova
authors.forename: Petra
authors.initials: P
authors.lastname: Reimerova
authors.forename: Jan
authors.initials: J
authors.lastname: Svec
authors.forename: Daniel
authors.initials: D
authors.lastname: Suchan
authors.forename: Miroslav
authors.initials: M
authors.lastname: Miletin
authors.forename: Hannah M
authors.initials: HM
authors.lastname: Rhoda
authors.forename: Victor N
authors.initials: VN
authors.lastname: Nemykin
authors.forename: Petr
authors.initials: P
authors.lastname: Zimcik
mesh_terms: D001372:Aza Compounds / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D004583:Electrons; D007211:Indoles / Q000737:chemistry*; D054833:Isoindoles; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D026082:Singlet Oxygen / Q000737:chemistry; D015032:Zinc / Q000737:chemistry*
chemical_list: D001372:Aza Compounds; D056831:Coordination Complexes; D007211:Indoles; D054833:Isoindoles; D009942:Organometallic Compounds; C483615:zinc naphthalocyanine; D026082:Singlet Oxygen; D015032:Zinc; C013647:phthalocyanine