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Title: Light-emitting platinum(ii) complexes supported by tetradentate dianionic bis(N-heterocyclic carbene) ligands : towards robust blue electrophosphors
Authors: Li, K
Cheng, G
Ma, C
Guan, X
Kwok, WM 
Chen, Y
Lu, W
Che, CM
Issue Date: 2013
Publisher: Royal Soc Chemistry
Source: Chemical science, 2013, v. 4, no. 6, p. 2630-2644 How to cite?
Journal: Chemical Science 
Abstract: The synthesis, structures and photophysical properties of the charge-neutral Pt(ii) complexes (1-6) and their Pd(ii) (7) and Ni(ii) (8) congeners supported by tetradentate dianionic bis[phenolate-(N-heterocyclic carbene)] ligands are described. The X-ray crystal structures of two solvatomorphs of 2, which has p-F substituents on the tetradentate ligand, have been determined. The photophysical properties of all the complexes were examined. In THF solutions, 1-4 display deep blue phosphorescence (λmax = ∼440-460 nm, Φe = 3-18% and τ = 0.5-3.5 μs). In solutions at room temperature, 5-8 show profoundly different luminescence properties from being virtually non-emissive (Φe < 10-3) for 6-8 to highly emissive (Φe = 15%) with much red-shifted phosphorescence (λmax = ∼530 nm) and a long emission lifetime (τ = 47.2 μs) in the case of 5. Time-dependent density functional theory (TDDFT) calculations reveal that the tetradentate bis(phenolate-NHC) ligands in 1-4 provide a rigid scaffold for preserving a tightly bound Pt(ii) in a square-planar coordination geometry in the T 1 as in the S0 states and the blue emission is derived from the T1 state having predominant ligand (πAr-O)-to- ligand (π*NHC) charge transfer (LLCT) character. A switch of orbital parentage from LLCT to ligand-centred (LC) π-π* is responsible for the long emission lifetime and vibronically structured emission displayed by 5 when compared to that of 1-4 and 6. Both femtosecond time-resolved fluorescence (fs-TRF) and nanosecond time-resolved emission (ns-TRE) measurements were conducted on 2 and 4 to directly probe the excited-state dynamics after photoexcitation. Excellent thermal stability of the fluorine-free complex 4 and its higher emission quantum yield (relative to 1 and 3), and using 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi) as host material, led to the fabrication of highly efficient deep blue OLEDs with peak current efficiency of 24 cd A-1 and white organic light-emitting devices (WOLEDs) with peak current efficiency of 88 cd A -1.
ISSN: 2041-6520
DOI: 10.1039/c3sc21822h
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