title: Near Infrared Phosphorescent, Non-oxidizable Palladium and Platinum Perfluoro-phthalocyanines.
abstract: New Pd(II) and Pt(II) complexes with a highly electron-deficient ligand (H2 PcF64 ) were conveniently prepared in a three-step synthesis. This is the first time that the phosphorescence of phthalocyanines with a H2 PcF64 framework has been measured. Based on these measurements, the triplet-state energies (ET ) were directly determined. Transient absorption experiments revealed broad T1 →Tn absorption spanning from ca. 350 to ca. 1000 nm and allowed determination of the triplet-state lifetimes. Removal of the Pd or Pt from the perfluoro-phthalocyanine resulted in a significant increase of the triplet lifetime for H2 PcF64 . The very efficient intersystem crossing observed for both PdPcF64 and PtPcF64 leads to residual fluorescence and suppresses the fluorescence lifetimes to less than 50 ps. The absence of Pd and Pt in the perfluoro-phthalocyanine ligand, viz. H2 PcF64 , led to a recovery of fluorescence. Cyclic voltamperometry studies pointed to complete resistance of PdPcF64 and PtPcF64 to oxidation and very strong electron affinity, which rendered these materials very good electron acceptors (n-type materials). The presence of d-orbital metals such as Pd(II) and Pt(II) in the phthalocyanine ring stabilizes their reduced forms, as indicated by the spectroelectrochemical experiments. PdPcF64 and PtPcF64 easily sensitize singlet oxygen production with very high quantum yields. Both phthalocyanines presented resistance to photodegradation in the solid state under aerobic conditions and under intense irradiation.
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060, Kraków, Poland. lapok@chemia.uj.edu.pl.
authors.forename: Łukasz
authors.identifier: http://orcid.org/0000-0002-7788-4321
authors.initials: Ł
authors.lastname: Łapok
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060, Kraków, Poland.
authors.forename: Magdalena
authors.initials: M
authors.lastname: Obłoza
authors.affiliation: Institute of Physical Chemistry, Polish Academy of Science, 44/52 Kasprzaka, 01-224, Warsaw, Poland.
authors.forename: Alexandr
authors.initials: A
authors.lastname: Gorski
authors.affiliation: B. I. Stepanov Institute of Physics, National Academy of Science, Independence Avenue 68, 220072, Minsk, Belarus.
authors.forename: Valeri
authors.initials: V
authors.lastname: Knyukshto
authors.affiliation: B. I. Stepanov Institute of Physics, National Academy of Science, Independence Avenue 68, 220072, Minsk, Belarus.
authors.forename: Tamara
authors.initials: T
authors.lastname: Raichyonok
authors.affiliation: Institute of Physical Chemistry, Polish Academy of Science, 44/52 Kasprzaka, 01-224, Warsaw, Poland.|Faculty of Mathematics and Science, Cardinal Stefan Wyszyński University, Dewajtis 5, 01-815, Warsaw, Poland.
authors.forename: Jacek
authors.initials: J
authors.lastname: Waluk
authors.affiliation: Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060, Kraków, Poland.
authors.forename: Maria
authors.initials: M
authors.lastname: Nowakowska
keywords: electron-deficient compounds; phosphorescence; phthalocyanines; semiconductors; singlet oxygen