No abstract

The synthesis, characterization, and photophysics of a series of solution-processable and strongly visible-light absorbing platinum(II) polyynes containing bithiazole-oligo(thienyl) rings were presented. Tuning the polymer solar cell efficiency, as well as optical and charge transport properties, in soluble, low-band gap PtII-based conjugated poly(heteroaryleneethynylene)s using the number of oligothienyl rings is described. These materials are highly soluble in polar organic solvents due to the presence of solubilizing bithiazole moieties and show strong absorptions in the solar spectra, rendering them excellent candidates for bulk heterojunction polymer solar cells. Their photovoltaic responses and power conversion efficiencies (PCEs) depend to a large extent on the number of thienyl rings along the main chain, and some of them can be used to fabricate highly efficient solar cells with PCEs of up to 2.7% and a peak external quantum efficiency to 83% under AM1.5 simulated solar illumination, which is comparable to that of poly(3-hexylthiophene)-based devices fabricated without additional processing (annealing or TiO(x) layer). The influence of the number of thienyl rings and the metal group on the performance parameters and optimization of solar cell efficiency was evaluated and discussed in detail. At the same blend ratio of 1:4, the light-harvesting ability and PCE increase sharply as the thienyl chain length increases. The present work provides an attractive approach to developing conjugated metallopolymers offering broad solar absorptions and tunable solar cell efficiency and demonstrates the potential of metalated conjugated polymers for efficient power generation.

The nature of Dexter triplet energy transfer between bonded systems of a red phosphorescent iridium complex 13 and a conjugated polymer, polyfluorene, has been investigated in electrophosphorescent organic light-emitting diodes. Red-emitting phosphorescent iridium complexes based on the [Ir(btp)(2)(acac)] fragment (where btp is 2-(2'-benzo[b]thienyl)pyridinato and acac is acetylacetonate) have been attached either directly (spacerless) or through a -(CH(2))(8)- chain (octamethylene-tethered) at the 9-position of a 9-octylfluorene host. The resulting dibromo-functionalized spacerless (8) or octamethylene-tethered (12) fluorene monomers were chain extended by Suzuki polycondensations using the bis(boronate)-terminated fluorene macromonomers 16 in the presence of end-capping chlorobenzene solvent to produce the statistical spacerless (17) and octamethylene-tethered (18) copolymers containing an even dispersion of the pendant phosphorescent fragments. The spacerless monomer 12 adopts a face-to-face conformation with a separation of only 3.6 A between the iridium complex and fluorenyl group, as shown by X-ray analysis of a single crystal, and this facilitates intramolecular triplet energy transfer in the spacerless copolymers 17. The photo- and electroluminescence efficiencies of the octamethylene-tethered copolymers 18 are double those of the spacerless copolymers 17, and this is consistent with suppression of the back transfer of triplets from the red phosphorescent iridium complex to the polyfluorene backbone in 18. The incorporation of a -(CH(2))(8)- chain between the polymer host and phosphorescent guest is thus an important design principle for achieving higher efficiencies in those electrophosphorescent organic light-emitting diodes for which the triplet energy levels of the host and guest are similar.