Platinum(II) Complexes with π‐Conjugated, Naphthyl‐Substituted, Cyclometalated Ligands (RC^N^N): Structures and Photo‐ and Electroluminescence

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Abstract
The crystal structures and photophysical properties of mononuclear [(RC^N^N)PtX](ClO4)n ((RC^N^N)=3‐(6′‐(2′′‐naphthyl)‐2′‐pyridyl)isoquinolinyl and derivatives; X=Cl, n=0; X=PPh3 or PCy3, n=1), dinuclear [(RC^N^N)2Pt2(μ‐dppm)](ClO4)2 (dppm=bis(diphenyphosphino)methyl) and trinuclear [(RC^N^N)3Pt3(μ‐dpmp)](ClO4)3 (dpmp=bis(diphenylphosphinomethyl)phenylphosphine) complexes are presented. The crystal structures show extensive intra‐ and/or intermolecular π⋅⋅⋅π interactions; the two (RC^N^N) planes of [(RC^N^N)2Pt2(μ‐dppm)](ClO4)2 (R=Ph, 3,5‐tBu2Ph or 3,5‐(CF3)2Ph) are in a nearly eclipsed configuration with torsion angles close to 0°. [(RC^N^N)PtCl], [(RC^N^N)2Pt2(μ‐dppm)](ClO4)2, and [(RC^N^N)3Pt3(μ‐dpmp)](ClO4)3 are strongly emissive with quantum yields of up to 0.68 in CH2Cl2 or MeCN solution at room temperature. The [(RC^N^N)PtCl] complexes have a high thermal stability (Td=470–549 °C). High‐performance light‐emitting devices containing [(RC^N^N)PtCl] (R=H or 3,5‐tBu2Ph) as a light‐emitting material have been fabricated; they have a maximum luminance of 63 000 cd m−2 and CIE 1931 coordinates at x=0.36, y=0.54.

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