title: Electrochemical, spectroscopic, and (1)O2 sensitization characteristics of 10,10-dimethylbiladiene complexes of zinc and copper.
abstract: The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethylbiladiene tetrapyrrole bearing ancillary pentafluorophenyl groups at the 5- and 15-meso positions (DMBil1) is presented. This nonmacrocyclic tetrapyrrole platform is robust and can serve as an excellent ligand scaffold for Zn(2+) and Cu(2+) centers. X-ray diffraction studies conducted for DMBil1 along with the corresponding Zn[DMBil1] and Cu[DMBil1] complexes show that this ligand scaffold binds a single metal ion within the tetrapyrrole core. Additionally, electrochemical experiments revealed that all three of the aforementioned compounds display an interesting redox chemistry as the DMBil1 framework can be both oxidized and reduced by two electrons. Spectroscopic and photophysical experiments carried out for DMBil1, Zn[DMBil1], and Cu[DMBil1] provide a basic picture of the electronic properties of these platforms. All three biladiene derivatives strongly absorb light in the visible region and are weakly emissive. The ability of these compounds to sensitize the formation of (1)O2 at wavelengths longer than 500 nm was probed. Both the free base and Zn(2+) 10,10-dimethylbiladiene architectures show modest efficiencies for (1)O2 sensitization. The combination of structural, electrochemical, and photophysical data detailed herein provides a basis for the design of additional biladiene constructs for the activation of O2 and other small molecules.
authors.affiliation: Department of Chemistry and Biochemistry, University of Delaware , Newark, Delaware 19716, United States.
authors.forename: Allen J
authors.initials: AJ
authors.lastname: Pistner
authors.forename: Rachel C
authors.initials: RC
authors.lastname: Pupillo
authors.forename: Glenn P A
authors.initials: GP
authors.lastname: Yap
authors.forename: Daniel A
authors.initials: DA
authors.lastname: Lutterman
authors.forename: Ying-Zhong
authors.initials: YZ
authors.lastname: Ma
authors.forename: Joel
authors.initials: J
authors.lastname: Rosenthal
mesh_terms: D002413:Cations, Divalent / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D004583:Electrons; D008027:Light; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D055668:Photochemical Processes; D013057:Spectrum Analysis; D045725:Tetrapyrroles / Q000737:chemistry*; D014961:X-Ray Diffraction; D015032:Zinc / Q000737:chemistry*
chemical_list: D002413:Cations, Divalent; D045725:Tetrapyrroles; D003300:Copper; D015032:Zinc; D010100:Oxygen