Michael J. Frampton

Control of Electrophosphorescence in Conjugated Dendrimer Light‐Emitting Diodes

We present a novel platinum porphyrin based phosphorescent dendrimer for use as a triplet harvesting dopant in organic light-emitting diodes. Two types of dendritic host materials are used. Through the choice of a common branching architecture around the emissive chromophore unit of both guest and host materials, we are able to achieve excellent miscibility. The relative contribution of guest to host emission is found to depend strongly on the energy level offsets of the two blend materials, indicating strong trapping processes. Under pulsed operation, we observe a striking dependence of the emission spectrum on pulse period, independent of the host material used. This spectral modification is attributed to the quenching of triplet excitations at high excitation densities. We find excellent agreement between our measured data and a model based on bimolecular recombination.

Stabilisation of a heptamethine cyanine dye by rotaxane encapsulation

The crystal structure of a cyanine dye rotaxane shows that the cyclodextrin is tightly threaded round the polymethine bridge of the dye; encapsulation dramatically increases the kinetic chemical stability of the radicals formed on oxidation and reduction of the dye, making it possible to observe the rotaxane radical dication by ESR and UV-vis-NIR spectroscopy.

The synthesis and properties of solution processable red-emitting phosphorescent dendrimers

We report methodology for the preparation of symmetric and asymmetric solution processable phosphorescent dendrimers that are comprised of 2-ethylhexyloxy surface groups, biphenyl based dendrons, and iridium(III) complex cores. The symmetric dendrimer has three dendritic 2-benzo[b]thiophene-2′-ylpyridyl (BTP) ligands with the dendritic ligands responsible for red emission. The asymmetric dendrimer has two dendritic 2-phenylpyridyl ligands and one unsubstituted BTP ligand. Iridium(III) complexes comprised of 2-phenylpyridyl ligands are normally associated with green emission whereas those containing BTP ligands emit red light. Red emission is observed from the asymmetric dendrimer demonstrating that emission occurs primarily from the metal-to-ligand charge transfer state associated with the ligand with the lowest HOMO–LUMO energy gap. The photoluminescence quantum yields (PLQYs) of the symmetric and asymmetric dendrimers were strongly dependent on the dendrimer structure. In solution the PLQYs of the asymmetric and symmetric dendrimers were 47 ± 5% and 29 ± 3% respectively. The photoluminescence lifetime of the emissive state of both dendrimers in solution was 7.3 ± 0.1 µs. In the solid state the comparative PLQYs were reversed with the symmetric dendrimer having a PLQY of 10 ± 1% and the asymmetric dendrimer a PLQY of 7 ± 1%. The comparatively larger decrease in PLQY for the asymmetric dendrimer in the solid state is attributed to increased core–core interactions. The intermolecular interactions are greater in the asymmetric dendrimer because there is no dendron on the BTP ligand. Electrochemical analysis shows that charge is injected directly into the cores of the dendrimers.

Laser action from a sugar-threaded polyrotaxane

We present gain and lasing results from a polyrotaxane consisting of a conjugated polymer (polyfluorene-alt-biphenylene) threaded through sugar macrocycles (β-cyclodextrin). Encapsulation suppresses interchain charge separation, leading to lasing emission not observed in the unthreaded polymer, and enlargement of the stimulated emission in threaded polymer is observed. We demonstrate all-optical switching distributed feedback laser.

Simple color tuning of phosphorescent dendrimer light emitting diodes

A simple way of tuning the emission color in solution processed phosphorescent organic light emitting diodes is demonstrated. For each color a single emissive spin-coated layer consisting of a blend of three materials, a fac-tris(2-phenylpyridyl)iridium (III) cored dendrimer (Ir–G1) as the green emitter, a heteroleptic [bis(2‐phenylpyridyl)‐2‐(2′‐benzo[4,5‐α]thienyl)pyridyl]iridium (III) cored dendrimer [Ir(ppy)2btp] as the red emitter, and 4,4′-bis(N-carbazolyl) biphenyl (CBP) as the host was employed. By adjusting the relative amount of green and red dendrimers in the blends, the color of the light emission was tuned from green to red. High efficiency two layer devices were achieved by evaporating a layer of electron transporting 1,3,5-tris(2-N-phenylbenzimidazolyl)benzene (TPBI) on top of the spin-coated emissive layer. A brightness of 100cd∕m2 was achieved at drive voltages in the range 5.3–7.3 V. The peak external efficiencies at this brightness ranged from 31cd∕A(18lm∕W) to 7cd∕A(4lm∕W).

The optoelectronic properties of electroluminescent dendrimers

Dendrimers can be used as the emissive layer in organic light-emitting diodes. We have synthesised conjugated dendrimers containing meta-linked stilbene dendrons and luminescent porphyrin or triarylamine cores. The HOMO energy levels of the amine-cored dendrimers were studied by cyclic voltammetry and modelling of device characteristics. Both techniques showed that charge was injected directly into the core and importantly that the energy levels did not change with dendrimer generation.

Structure-property relationships in conjugated molecules

Conjugated dendrimers are ideal materials to study the structure-property relationships in conjugated molecules. We have developed a family of dendrimers that contain t-butyl surface groups, stilbene dendrons, and luminescent cores. For porphyrin and tris(distyrylbenzenyl) amine cored dendrimers cyclic voltammetry (CV) showed that the redox processes occurred at the core. Combining the results from the CV experiments with the device characteristics it was determined that for the dendrimers the cores were held further away from each other with increasing generation. For the amine cored dendrimers it was found that the hole mobility decreased with generation, which is consistent with the cores being further apart. We also found for the amine cored dendrimers that the decrease in hole mobility was matched with increase in device efficiency

Photoexcitation dynamics in thin films of insulated molecular wires

A study is presented on how encapsulation of conjugated polymer chains affects the motion of photoexcitations and the formation of interchain aggregates in solid films. It is shown that threading of a poly(diphenylene vinylene) backbone inside insulating cyclodextrins (rotaxination) and/or complexation of the chains with poly(ethylene oxide) are effective means of preventing the diffusion of excitons to nonradiative defect sites. Ultrafast time-resolved photoluminescence data reveal that excitation transfer between encapsulated chains is still possible and, for the case of rotaxination, is likely to be facilitated through close packing of end groups belonging to adjacent chains.

The effect of intermolecular interactions on the electro-optical properties of porphyrin dendrimers with conjugated dendrons

We have synthesised a new family of dendrimers with stilbene dendrons attached to a porphyrin core via a stilbene unit and compared their properties with a family of dendrimers with the same core and dendrons but with the dendrons attached via a phenyl unit. The oxidation and reduction half potentials of the two dendrimer families were found to be the same and independent of generation indicating that the dendrons were not creating a micro-environment for the core. However, the rate of heterogeneous electron transfer was found to be strongly dependent on link type and generation. The photoluminescence quantum yield (PLQY) of the dendrimers was also found to be strongly dependent on the method of attachment of the core. In solution the dendrimers with the stilbene link between core and dendrons had PLQYs 1.5 times higher than their phenyl counterparts but in the solid state the trend was reversed with the phenyl linked dendrimers generally having a higher PLQY. The difference in properties has been assigned to the comparative openness of the dendrimer architectures and the effect of the dendrons on the shape of the porphyrin core.

67.1: Invited Paper: Dendrimers — Efficient Solution‐Processed Phosphorescent OLED Materials

Three aspects of recent dendrimer research are reported. It is shown that highly efficient sky blue phosphorescent devices can be made (external efficiency 10.4%, 11 lm/W at 100 Cd/m), that blending dendrimers provides a simple way of colour tuning, and finally that luminescence quenching by exciton-exciton annihilation in dendrimer films is weak and can be controlled by the dendrimer generation. These results suggest that dendrimers are very attractive solution processible materials for OLEDs.