title: Tuning the Structure and Photophysics of a Fluorous Phthalocyanine Platform.
abstract: Phthalocyanines are an important class of industrial dyes with potential commercial applications ranging from photovoltaics to biomedical imaging and therapeutics. We previously demonstrated the versatility of the commercially available zinc(II) hexadecafluorophthalocyanine (ZnF16Pc) as a platform for rapidly developing functional materials for these applications and more. Because this core-platform approach to dye development is increasingly common, it is important to understand the photophysical and structural consequences of the substitution chemistry involved. We present a fundamental study of a series of ZnF16Pc derivatives in which the aromatic fluorine atoms are progressively substituted with thioalkanes. Clear spectroscopic trends are observed as the substituents change from electron-withdrawing to electron-releasing groups. Additionally, there is evidence for significant structural distortion of the normally planar heterocycle, with important ramifications for the photophysics. These results are also correlated to DFT calculations, which show that the orbital energies and symmetries are both important factors for explaining the excited-state dynamics.
authors.affiliation: Department of Chemistry, Hunter College of the City University of New York , New York, New York 10065, United States.|Department of Chemistry, The Graduate Center of the City University of New York , New York, New York 10016, United States.
authors.forename: Christopher
authors.initials: C
authors.lastname: Farley
authors.affiliation: Department of Chemistry, Hunter College of the City University of New York , New York, New York 10065, United States.
authors.forename: N V S Dinesh K
authors.initials: NV
authors.lastname: Bhupathiraju
authors.affiliation: Department of Chemistry, Hobart and William Smith Colleges , Geneva, New York 14456, United States.
authors.forename: Bianca K
authors.initials: BK
authors.lastname: John
authors.affiliation: Department of Chemistry, Hunter College of the City University of New York , New York, New York 10065, United States.|Department of Chemistry, The Graduate Center of the City University of New York , New York, New York 10016, United States.|The Rockefeller University , New York, New York 10065, United States.
authors.forename: Charles Michael
authors.initials: CM
authors.lastname: Drain
mesh_terms: D003198:Computer Simulation; D004583:Electrons; D005461:Fluorine / Q000737:chemistry / Q000528:radiation effects; D007211:Indoles / Q000138:chemical synthesis* / Q000737:chemistry*; D054833:Isoindoles; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D015394:Molecular Structure; D055668:Photochemical Processes; D013056:Spectrophotometry, Ultraviolet
chemical_list: D007211:Indoles; D054833:Isoindoles; D005461:Fluorine; C013647:phthalocyanine