TY - JOUR
T1 - Porphyrin/Platinum(II) C^N^N Acetylide Complexes
T2 - Synthesis, Photophysical Properties, and Singlet Oxygen Generation
AU - Jana, Atanu
AU - McKenzie, Luke
AU - Wragg, Ashley B.
AU - Ishida, Masatoshi
AU - Hill, Jonathan P.
AU - Weinstein, Julia A.
AU - Baggaley, Elizabeth
AU - Ward, Michael D.
PY - 2016/3/14
Y1 - 2016/3/14
N2 - 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).
AB - 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).
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U2 - 10.1002/chem.201504509
DO - 10.1002/chem.201504509
M3 - Article
AN - SCOPUS:84960192090
VL - 22
SP - 4164
EP - 4174
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 12
ER -