We report the synthesis and properties of p-stacked polymers consisting of oligothiophene and naphthalene as the stacked p-system and the scaffold, respectively. The titled polymers were obtained by the Suzuki-Miyaura coupling reaction. Oligothiophene units were layered in proximity, B3.0 Å from each other. Contribution of the quinoidal structure of the oligothiophene units involving the naphthalene scaffolds in the excited state resulted in relatively high photoluminescence quantum efficiencies. The polymers have potential application to optoelectronic devices such as hole-transporting materials. Polymer Journal (2010) 42, 928-934; doi:10.1038/pj.2010.101; published online 27 October 2010Keywords: conjugated polymers; p-stacked polymers; oligothiophene; redox polymers; synthesis
INTRODUCTIONCommon conjugated polymers generally consist of sp-and/or sp 2 -carbon frameworks, and p-electrons are delocalized throughout the polymer backbone. Such conjugated polymers have attracted considerable attention because of their good processability and their readily tunable electronic and optical properties. [1][2][3] Recently, a new type of conjugated polymer that exhibits through-space interactions of pelectron systems has been developed. Poly(dibenzofulvene)s, 4-11 7,7-diarylnorbornane-containing conjugated polymers, 12,13 cyclophanecontaining polymers and face-to-face ferrocene polymers [36][37][38] have been synthesized, and their optical and electrochemical properties have been studied in detail. Polymers with layered aromatic rings and p-electron systems have also been investigated; 39-53 for example, Chen et al. 53 recently reported the synthesis and formation of a twodimensional assembly of polymeric ladder phanes containing face-toface p-electron systems. These polymers have potential applications in optoelectronic devices and single-molecular devices such as singlemolecular wires.Cofacially aligned p-electron systems have an important role in biochemistry and material chemistry; DNA has face-to-face base pairs stacked in the double-stranded main chains, 54 and the performance of organic optoelectronic devices strongly depends on the arrangement of the p-electron systems. 55 We have recently reported the synthesis of aromatic-ring-layered polymers using xanthene compounds as scaffolds. [40][41][42][43][44][45][46][47] [2.2] Paracyclophane-layered polymers, which mimic multilayered cyclophanes, 56-59 exhibited fluorescence resonance energy transfer from the layered paracyclophanes to the end-capping groups. The use of xanthene as a scaffold enabled us to introduce various aromatic compounds, such as phenylenes, 44 carbazoles, 45 thiophenes 46 and anthracene, 47 into the polymers, with the distance between the layered aromatic units being B4.5 Å . Our next target is to construct layered and p-stacked aromatic systems in proximity, less than the sum of the van der Waals radius (3.40 Å ) of an sp 2 -carbon, in the polymer backbone.