Abstract
We demonstrate control of the photoluminescence spectra and decay rates of water-soluble green-emitting conjugated polyrotaxanes by incorporating them in polystyrene opals with a stop-band spectrally tuned on the rotaxane emission (405–650 nm). We observe a suppression of the luminescence within the photonic stop-band and a corresponding enhancement of the high-energy edge (405–447 nm). Time-resolved measurements reveal a wavelength-dependent modification of the emission lifetime, which is shortened at the high-energy edge (by ∼11%, in the range 405–447 nm), but elongated within the stop-band (by ∼13%, in the range 448–482 nm). We assign both effects to the modification of the density of photonic states induced by the photonic crystal band structure. We propose the growth of fluorescent composite photonic crystals from blends of “solvent-compatible” non-covalently bonded nanosphere-polymer systems as a general method for achieving a uniform distribution of polymeric dopants in three-dimensional self-assembling photonic structures.
Highlights
Self-assembled Photonic crystals (PhCs) have been studied in detail due to their low cost of fabrication and ease of preparation, with artificial opals[1,2,8,9] being especially popular
Processability of the active materials is obviously crucial to their incorporation into organic PhC, and, interestingly, water-soluble conjugated polymers with high photoluminescence (PL) efficiency provide an intriguing opportunity for use in combination with plastic PhC templates, but only a few attempts have been reported so far.[19,20,21,22]
Conjugated polyelectrolytic rotaxanes[23] (Fig. 1) offer a very interesting class of materials to incorporate into PhCs since they benefit from a supramolecular architecture in which conjugated backbones such as poly(4,4 -diphenylene vinylene) (PDV) are threaded through cyclodextrin rings (β-CD), that sterically impose increased intermolecular distances
Summary
Photonic crystals (PhCs)[1,2] have been widely investigated over the last two decades and are proposed in applications such as light-emitting diodes (LEDs),[3] solar cells,[4,5] and lasers.[6,7] Among them, self-assembled PhCs have been studied in detail due to their low cost of fabrication and ease of preparation, with artificial opals[1,2,8,9] being especially popular. 2(a) and 2(b) show no presence of lattice distortion induced by the incorporation of polyrotaxanes, nor an excess polymer layer on the opal surface for co-grown PhCs with 8 × 10−3 mg/ml PDV.Li⊂β-CD solution and, more importantly, 042116-4 Di Stasio et al.
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