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Anionic cyclometallated Pt(II) square-planar complexes: new sets of highly luminescent compounds

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Abstract

Two series of novel NBu4+ salts of anionic cyclometallated Pt(II) complexes were synthesized and fully characterized. These highly luminescent compounds (NBu4[(C^N)Pt(O^N)] and NBu4[(C^N)Pt(O^O)]) are incorporated as testing examples of cyclometallating ligands 2-phenylpyridine (PhPy), 2-(2,4-difluorophenyl)-pyridine (F2PhPy) and 2-thienylpyridine (ThPy), and a benzo[h]quinoline (Bzq) fragment. All complexes display a square-planar coordination sphere, wherein the “(C^N)Pt” fragment is completed either by an O^N orotate (Ort) or an O^O tetrabromocatecholate (Cat) ligand. The HOMO and LUMO levels of all complexes were estimated by cyclic voltammetry and a comprehensive electrochemical and photophysical study was performed. The new complexes are emissive in solution at 298 K and the NBu4[(ThPy)Pt(Ort)] complex displays good photosensitizing properties (Φ = 28% in deaerated solution vs. Φ = 1.4% in the presence of O2). Both series of NBu4[(C^N)Pt(Ort)] and NBu4[(C^N)Pt(Cat)] complexes are highly luminescent in the solid state (emission quantum yields from 10 to 85%). Remarkably, the square-planar Pt(II) anionic complexes showed an important increase in luminescence quantum yields on changing from the dilute solution to the solid state (the most significant from 0.13% to 85% for the NBu4[(PhPy)Pt(Ort)] complex, an ideal candidate as an active species for LEECs).

Graphical abstract: Anionic cyclometallated Pt(ii) square-planar complexes: new sets of highly luminescent compounds

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Publication details

The article was received on 22 Jun 2017, accepted on 25 Aug 2017 and first published on 25 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT02267K
Citation: Dalton Trans., 2017, Advance Article
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    Anionic cyclometallated Pt(II) square-planar complexes: new sets of highly luminescent compounds

    L. Ricciardi, M. La Deda, A. Ionescu, N. Godbert, I. Aiello and M. Ghedini, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02267K

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