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Chemistry. 2016 Mar 14;22(12):4164-74. doi: 10.1002/chem.201504509. Epub 2016 Feb 5.

Porphyrin/Platinum(II) C^N^N Acetylide Complexes: Synthesis, Photophysical Properties, and Singlet Oxygen Generation.

Author information

1
Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, United Kingdom. atanu.j78@gmail.com.
2
Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, United Kingdom.
3
Education Center for Global Leaders in Molecular Systems for Devices, Kyushu University, Fukuoka, 819-0395, Japan.
4
World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), Namiki (Tsukuba, Ibaraki, 305-0044, Japan.
5
Department of Chemistry, University of Sheffield, Sheffield, S3 7HF, United Kingdom. m.d.ward@sheffield.ac.uk.

Abstract

A new class of substituted porphyrins has been developed in which a different number of cyclometalated Pt(II) 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 ((1)O2) generation studies. All of these Zn(II) porphyrin-Pt(II) 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 Pt(II) C^N^N antenna units to the Zn(II) porphyrin core, which shows sensitized luminescence, as shown by quenching of Pt(II) C^N^N-based luminescence. Electrochemical measurements show a set of redox processes that are approximately the sum of what is observed for the Pt(II) C^N^N acetylide and Zn(II) porphyrin units. UV/Vis spectroscopic properties are supported by DFT calculations.

KEYWORDS:

acetylide complexes; energy transfer; platinum; porphyrins; singlet oxygen; zinc

PMID:
26849274
DOI:
10.1002/chem.201504509

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