title: β-Functionalized Push-Pull opp-Dibenzoporphyrins.
abstract: The synthesis of a series of β-functionalized push-pull dibenzoporphyrins was realized. These porphyrins display subtle push-pull effects, demonstrating the exceptional tunability of their electronic and electrochemical properties. The UV-vis spectra of these porphyrins show unique absorption patterns with shouldered Soret bands and extra absorptions in the Q-band region. Stronger electron-withdrawing groups display more significant bathochromic shifts of the Soret bands. The fluorescence spectra of these porphyrins show strong near-IR emission bands (600-850 nm). In particular, fluorescence quenching effect was observed for pyridyl carrying push-pull porphyrin 4c in the presence of an acid. TFA titration study of 4c using UV-vis and fluorescence spectroscopy reveals that the fluorescence quenching can be mainly attributed to the protonation of the pyridyl groups of 4c. The versatile synthetic methods developed in this work may open a door to access a large number of functionalized organic materials that are currently unavailable. The structure-property studies provided in this work may provide useful guidelines for the design of new generations of materials in dye-sensitized solar cells, in nonlinear optical applications, as fluorescence probes, as well as sensitizers for photodynamic therapy.
authors.affiliation: Department of Chemistry and Biochemistry, Miami University , 701 E High Street, Oxford, Ohio 45056, United States.
authors.forename: R G Waruna
authors.initials: RG
authors.lastname: Jinadasa
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Yuanyuan
authors.initials: Y
authors.lastname: Fang
authors.affiliation: Department of Chemistry and Biochemistry, Miami University , 701 E High Street, Oxford, Ohio 45056, United States.
authors.forename: Siddhartha
authors.initials: S
authors.lastname: Kumar
authors.affiliation: Department of Chemistry, University of Akron , Akron, Ohio 44325, United States.
authors.forename: Allen J
authors.initials: AJ
authors.lastname: Osinski
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Xiaoqin
authors.initials: X
authors.lastname: Jiang
authors.affiliation: Department of Chemistry, University of Akron , Akron, Ohio 44325, United States.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Ziegler
authors.affiliation: Department of Chemistry, University of Houston , Houston, Texas 77204-5003, United States.
authors.forename: Karl M
authors.initials: KM
authors.lastname: Kadish
authors.affiliation: Department of Chemistry and Biochemistry, Miami University , 701 E High Street, Oxford, Ohio 45056, United States.
authors.forename: Hong
authors.initials: H
authors.lastname: Wang