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Title: Electrochemical, Spectroscopic and 1O2 Sensitization Characteristics of 10,10-Dimethylbiladiene Complexes of Zinc and Copper

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 non-macrocyclic 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 1O 2 at wavelengths longer than 500 nm was probed. Both the freebase and Zn 2+ 10,10-dimethylbiladiene architectures show modest efficiencies for 1O 2 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 O 2more » and other small molecules.« less
 [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [1]
  1. Univ. of Delaware, Newark, DE (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
Published Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 118; Journal Issue: 45; Journal ID: ISSN 1089-5639
American Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
OSTI Identifier:
Alternate Identifier(s):
OSTI ID: 1185659