A poly(styrene) with pendant dendronized iridium(III) complexes attached to every repeat unit was prepared in good yields using a free radical polymerization of a "macromonomer". The dendronized pendant groups were heteroleptic iridium(III) complexes comprised of two 2-phenylpydridyl ligands, to which first generation biphenyl dendrons with 2-ethylhexyloxy surface groups were attached, and a phenyltriazolyl coligand that formed the attachment point to the polymer backbone. Dendronization of the pendant iridium(III) complexes was found to improve thermal stability, solubility, and solution (61%) and solid-state (13%) photoluminescence quantum yields (PLQYs) relative to the nondendronized homopolymer. Viscosity under normal solution processing conditions of 25 mg/mL was found to be 1.23 cSt. Importantly, although the phosphorescent iridium(III) chromophores are held closely along the polymer backbone, they do not significantly reduce the PLQY in solution by intrachain chromophore interactions. Simple bilayer organic light-emitting diodes comprising a blend of the poly(dendrimer) with 4,4-bis(N-carbazolyl)biphenyl and an electron transporting layer had good performance with an external quantum efficiency of 6.2% at 100 cd/m 2 .
The reaction of N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold hydroxide ([Au(OH)(IPr)]; 1) with acetylene and trimethylsilylacetylene derivatives cleanly leads to the formation of a gold-acetylide bond with the concomitant formation of water or trimethylsilanol. All compounds were isolated in high yield (>85%). The crystal structures of selected gold acetylides in conjunction with their UV-vis absorption/emission properties were investigated. Finally, DFT calculations were performed in an attempt to gain an insight into the mechanism of the general reaction.
A norbornenyl-based homopolymer that has a dendronised iridium(III) complex attached to every monomer unit has been synthesized. The dendronised iridium(III) complex is comprised of three facially arranged 2-phenylpyridyl ligands. Two of the ligands bear first generation biphenyl-based dendrons with 2-ethylhexyloxy surface groups attached and the third ligand is attached to the polymer backbone via a benzyloxy ester. The polymer was formed by ring opening metathesis using the Grubbs III catalyst and was found to have an M p of 130 kDa by MALDI-TOF mass spectrometry. At a concentration of 25 mg cm À3 the polymer solution had a viscosity of 1.09 mPa s, which was 34% higher than a solution containing a dendrimer of same weight per volume. The dendrimer had the same core, dendrons, and surface groups but differed from the polymer in that it had dendrons attached to three of the ligands rather than the two of the polymer. The solution photoluminescence quantum yield (PLQY) of the poly(dendrimer) was found to be 57%, indicating that intra-polymer chromophore interactions were not leading to strong quenching of the luminescence. However, in the solid-state the PLQY dropped significantly, indicating that inter-polymer chromophore interactions were significant. The presence of the dendrons allowed the simple blending of the polymer with 4,4 0 -bis(N-carbazolyl)-2,2 0 -biphenyl (CBP), and the blended film had a PLQY of 50%. Simple bilayer devices with a blended emissive layer and an electron injection and transport layer had an external quantum efficiency of 6.2% at a brightness of 100 cd m À2 , showing that poly(dendrimer)s are a promising class of OLED material.
1,4,5,8,9,12-hexamethyltriphenylene (HMTP) shows a high photoluminescence quantum yield (PLQY) of 31% in the solid state, making it of interest for luminescence applications. The detailed photophysical properties of HMTP have been investigated by using time-resolved and steady-state luminescence, PLQY, and molar absorption coefficient measurements. An enhancement of the transition dipole moment for fluorescence and absorption was demonstrated compared to the case of unsubstituted triphenylene, which resulted in a 20-fold increase in the radiative decay rate. This is attributed to a breaking of triphenylene symmetry as a result of the necessarily twisted structure induced by steric crowding. In addition, it was shown that HMTP shows similar photoluminescence energies in solution, powder, and film, indicating a reduced propensity for intermolecular π-stacking compared to the case of triphenylene, as a result of this twisted structure. This work also develops a method for calculating the photoluminescence quantum yield of powders by using a calibrated photodiode in combination with an uncalibrated CCD spectrometer.
A method employing conjugated polymer thin film blends is shown to provide a simple and convenient way of greatly enhancing the ultraviolet response of silicon photodetectors. Hybrid organic semiconductor/silicon photodetectors are demonstrated using fluorene copolymers and give a quantum efficiency of 60% at 200 nm. The quantum efficiency is greater than 34% over the entire 200-620 nm range. These devices show promise for use in high sensitivity, low cost UV-visible photodetection and imaging applications.
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