Porphyrin/Platinum(II) C^N^N Acetylide Complexes

Synthesis, Photophysical Properties, and Singlet Oxygen Generation

Atanu Jana, Luke McKenzie, Ashley B. Wragg, Masatoshi Ishida, Jonathan P. Hill, Julia A. Weinstein, Elizabeth Baggaley, Michael D. Ward

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

A new class of substituted porphyrins has been developed in which a different number of cyclometalated PtII C^N^N acetylides and polyethylene glycol (PEG) chains are attached to the meso positions of the porphyrin core, which are meant for photophysical, electrochemical, and in vitro light-induced singlet oxygen (1O2) generation studies. All of these ZnII porphyrin-PtII C^N^N acetylide conjugates show moderate to high (ΦΔ=0.55 to 0.63) singlet oxygen generation efficiency. The complexes are soluble in organic solvents but, despite the PEG substituents, slowly aggregate in aqueous solvent systems. These conjugates also exhibit interesting photophysical properties, including near-complete photoinduced energy transfer (PEnT) through the rigid acetylenic bond(s) from the PtII C^N^N antenna units to the ZnII porphyrin core, which shows sensitized luminescence, as shown by quenching of PtII C^N^N-based luminescence. Electrochemical measurements show a set of redox processes that are approximately the sum of what is observed for the PtII C^N^N acetylide and ZnII porphyrin units. UV/Vis spectroscopic properties are supported by DFT calculations. The photophysical, electrochemical, and light-induced singlet oxygen (1O2) generation properties are reported for a series of ZnII porphyrin/PtII C^N^N acetylide compounds. One, two, or three cyclometallated PtII C^N^N luminophores are grafted onto a ZnII porphyrin core (see figure; R=PEG chain).

Original languageEnglish
Pages (from-to)4164-4174
Number of pages11
JournalChemistry - A European Journal
Volume22
Issue number12
DOIs
Publication statusPublished - Mar 14 2016

Fingerprint

Singlet Oxygen
Porphyrins
Platinum
Oxygen
Polyethylene glycols
Luminescence
Discrete Fourier transforms
Energy transfer
Organic solvents
Quenching
Antennas

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Porphyrin/Platinum(II) C^N^N Acetylide Complexes : Synthesis, Photophysical Properties, and Singlet Oxygen Generation. / Jana, Atanu; McKenzie, Luke; Wragg, Ashley B.; Ishida, Masatoshi; Hill, Jonathan P.; Weinstein, Julia A.; Baggaley, Elizabeth; Ward, Michael D.

In: Chemistry - A European Journal, Vol. 22, No. 12, 14.03.2016, p. 4164-4174.

Research output: Contribution to journalArticle

Jana, Atanu ; McKenzie, Luke ; Wragg, Ashley B. ; Ishida, Masatoshi ; Hill, Jonathan P. ; Weinstein, Julia A. ; Baggaley, Elizabeth ; Ward, Michael D. / Porphyrin/Platinum(II) C^N^N Acetylide Complexes : Synthesis, Photophysical Properties, and Singlet Oxygen Generation. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 12. pp. 4164-4174.
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