Increasing the horizontal orientation of transition dipole moments in solution processed small molecular emitters.

The efficiency of organic light emitting diodes (OLEDs) can be improved by controlling the orientation of the transition dipole moment of the emitters. Currently, no effective methods exist for orienting the transition dipole moments in solution processed active layers for OLEDs. We investigate the orientation of the transition dipole moment of small molecular emitters in a host matrix of poly(9,9-dioctylfluorene) (PFO) by means of angle dependent luminescence intensity measurements. The polymer chains of the host orient predominantly in the plane of the film. Fluorescent p-phenylenevinylene oligomers with 6 and 7 repeat units (OPV6, OPV7) are found to also orient preferentially horizontally. The orientation of the emitters can be improved by thermal annealing with up to 90% of transition dipole moments oriented in the plane of the film. The phosphorescent emitter Ir(MDQ)2(acac) shows a degree of horizontal orientation in the polymeric host matrix lower than that which is observed for oligomers, but as high as is observed for the same emitter in evaporated layers. A carbazole derivative capable of thermally activated delayed fluorescence shows a small preference for vertical orientation within the polymer host. The strong orientation of OPV6 and OPV7 in the oriented polymer host is rationalized in terms of their high aspect ratios. The use of PFO as host material in host/guest systems allows achieving horizontal orientation of transition dipole moments in solution processed oligomers and small molecular emitters.

The role of C-H and C-C stretching modes in the intrinsic non-radiative decay of triplet states in a Pt-containing conjugated phenylene ethynylene.

The intrinsic non-radiative decay (internal conversion) from the triplet excited state in phosphorescent dyes can be described by a multi-phonon emission process. Since non-radiative decay of triplet excitons can be a significant process in organic light-emitting diodes, a detailed understanding of this decay mechanism is important if the overall device efficiency is to be controlled. We compare a deuterated Pt(II)-containing phenylene ethynylene with its non-deuterated counterpart in order to investigate which phonon modes control to the non-radiative decay path. We observe that deuteration does not decrease the non-radiative decay rate. A Franck-Condon analysis of the phosphorescence spectra shows that the electronic excitation is coupled strongly to the breathing mode of the phenyl ring and the C≡C carbon stretching modes, while high-energy C-H or C-D stretching modes play an insignificant role. We, therefore, associate the internal conversion process with the carbon-carbon stretching vibrations.

Synthesis of conjugated polyrotaxanes.

A series of conjugated polyrotaxane insulated molecular wires are synthesised by aqueous Suzuki polymerisation, using hydrophobic binding to promote threading of the cyclodextrin units. These polyrotaxanes have conjugated polymer cores based on poly(para-phenylene), polyfluorene, and poly(diphenylene-vinylene), threaded through 0.9-1.6 cyclodextrins per repeat unit. Bulky naphthalene-3,6-disulfonate endgroups prevent the macrocycles from slipping off the conjugated polymer chains. Dialysis experiments show that the cyclodextrins become unthreaded only if smaller stoppers are used. MALDI TOF mass spectra detect oligomers with up to ten threaded cyclodextrins, and reveal the presence of some defects that result for oxidative homo-coupling of boronic acids. Weight-average molecular weights were determined by analytical ultracentrifugation, demonstrating that step-growth polymerisation is efficient enough to achieve degrees of polymerisation up to approximately 20 repeat units (84 para-phenylenes). The fluorescence spectra of these polyrotaxanes indicate that the presence of the threaded cyclodextrin macrocycles reduces the flexibility of the conjugated polymer pi-systems. Both the solution and the solid-state photoluminescence quantum yields are enhanced upon threading of the conjugated polyaromatic cores through alpha- or beta-cyclodextrins, and the emission spectra of the polyrotaxanes are blue-shifted compared to the corresponding unthreaded polymers. The greater weight of the 0-0 transition in the emission spectra, as well as the smaller Stokes shift, indicate that the polyrotaxanes are more rigid than the unthreaded polymers.

Cyclodextrin-threaded conjugated polyrotaxanes as insulated molecular wires with reduced interstrand interactions.

Control of intermolecular interactions is crucial to the exploitation of molecular semiconductors for both organic electronics and the viable manipulation and incorporation of single molecules into nano-engineered devices. Here we explore the properties of a class of materials that are engineered at a supramolecular level by threading a conjugated macromolecule, such as poly(para-phenylene), poly(4,4'-diphenylene vinylene) or polyfluorene through alpha- or beta-cyclodextrin rings, so as to reduce intermolecular interactions and solid-state packing effects that red-shift and partially quench the luminescence. Our approach preserves the fundamental semiconducting properties of the conjugated wires, and is effective at both increasing the photoluminescence efficiency and blue-shifting the emission of the conjugated cores, in the solid state, while still allowing charge-transport. We used the polymers to prepare single-layer light-emitting diodes with Ca and Al cathodes, and observed blue and green emission. The reduced tendency for polymer chains to aggregate allows solution-processing of individual polyrotaxane wires onto substrates, as revealed by scanning force microscopy.