Electrochemical, Spectroscopic, and 1 O 2 Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

• Published in: Inorganic chemistry 2017-11, Vol.56 (21), p.12703-12711
• Main Authors: Potocny, Andrea M, Pistner, Allen J, Yap, Glenn P A, Rosenthal, Joel
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.7b00796

The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethyl-5,15-bis(pentafluorophenyl)biladiene (DMBil1) linear tetrapyrrole supporting Pd or Pt centers is presented. Both of these nonmacrocyclic tetrapyrrole platforms are robust and easily prepared via modular routes. X-ray diffraction experiments reveal that the Pd[DMBil1] and Pt[DMBil1] complexes adopt similar structures and incorporate a single Pd and Pt center, respectively. Additionally, electrochemical experiments revealed that both Pd[DMBil1] and Pt[DMBil1] can undergo two discrete oxidation and reduction processes. Spectroscopic experiments carried out for Pd[DMBil1] and Pt[DMBil1] provide further understanding of the electronic structure of these systems. Both complexes strongly absorb light in the UV-visible region, especially in the 350-600 nm range. Both Pd[DMBil1] and Pt[DMBil1] are luminescent under a nitrogen atmosphere. Upon photoexcitation of Pd[DMBil1], two emission bands are observed; fluorescence is detected from ∼500-700 nm and phosphorescence from ∼700-875 nm. Photoexcitation of Pt[DMBil1] leads only to phosphorescence, presumably due to enhanced intersystem crossing imparted by the heavier Pt center. Phosphorescence from both complexes is quenched under air due to energy transfer from the excited triplet state to ground state oxygen. Accordingly, irradiation with light of λ ≥ 500 nm prompts Pd[DMBil1] and Pt[DMBil1] to photosensitize the generation of O (singlet oxygen) with impressive quantum yields of 80% and 78%, respectively. The synthetic accessibility of these complexes coupled with their ability to efficiently photosensitize O may make them attractive platforms for development of new agents for photodynamic therapy.