A series of ten cationic complexes
of the general formula [(C^C)Au(P^P)]X,
where C^C = 4,4′-di-tert-butyl-1,1′-biphenyl,
P^P is a diphosphine ligand, and X is a noncoordinating counteranion,
have been synthesized and fully characterized by means of chemical
and X-ray structural methods. All the complexes display a remarkable
switch-on of the emission properties when going from a fluid solution
to a solid state. In the latter, long-lived emission with lifetime
τ = 1.8–83.0 μs and maximum in the green-yellow
region is achieved with moderate to high photoluminescence quantum
yield (PLQY). This emission is ascribed to an excited state with a
mainly triplet ligand-centered (3LC) nature. This effect
strongly indicates that rigidification of the environment helps to
suppress nonradiative decay, which is mainly attributed to the large
molecular distortion in the excited state, as supported by density
functional theory (DFT) and time-dependent DFT (TD-DFT) computation.
In addition, quenching intermolecular interactions of the emitter
are avoided thanks to the steric hindrance of the substituents. Emissive
properties are therefore restored efficiently. The influence of both
diphosphine and anion has been investigated and rationalized as well.
Using two complexes as examples and owing to their enhanced optical
properties in the solid state, the first proof-of-concept of the use
of gold(III) complexes as electroactive materials for the fabrication
of light-emitting electrochemical cell (LEC) devices is herein demonstrated.
The LECs achieve peak external quantum efficiency, current efficiency,
and power efficiency up to ca. 1%, 2.6 cd A–1, and 1.1 lm W–1 for complex 1PF6
and 0.9%, 2.5 cd A–1, and 0.7 lm W–1 for complex 3, showing the potential
use of these novel emitters as electroactive compounds in LEC devices.