| Summary: | 碩士 === 國立中山大學 === 材料與光電科學學系研究所 === 100 === A series of stereoregular polymers including atactic, syndiotactic and isotactic poly 4(N, N-diphenyl)styrene (PNNDPS) and poly 4(N, N-ethylphenyl)styrene (PNNEPS) were synthesized to exam the tacticity effect on the photoluminescence (PL) behavior. Also, different degrees of the regularity as well as the chemical modification of the fluorophor were explored in the stereoregular polymers. Because of the increase of the steric hindrance among the bulky triphenylamine pendants in the polymer chains, a red shift of the PL emission with an accompanying increase in the emissive intensity was found in contrast to the weakened emission of triphenylamine monomers.
In solution state, the PL spectra of these stereoregular polymers reveal multiple PL emissive bands including monomeric and aggregation emissions as evidenced by the time-resolved lifetime measurement. Because of the huge triphenylamine pendants, the triphenylamine pendants attached on the iPNNDPS17 (mmmmmm~50%) might encounter higher steric hindrance than that in the sPNNDPS23 (rrrrrr~59%) due to the stereoregularity evidenced by simulation. Accordingly, the iPNNDPS17 (mmmmmm~50%) exhibits more emissive intensity than the sPNNDPS23 (rrrrrr~59%) due to the effective blockage of the intramolecular rotation of the phenyl blade i.e., the restriction of intramolecular rotation (RIR). Accordingly, the RIR-active PNNDPS is highly sensitive to the temperature variations.
The chemical modification of the fluorophor was carried out to examine the effect of the chemical structure. By comparison, the sPNNDPS2 (rrrrrr~70%) with high regularity exhibits much higher emissive intensity than the sPNNDPS23 (rrrrrr~59%) with low regularity due to the less solubility. However, more intense PL emission can be found in the sPNNEPS17 than aPNNEPS8 due to the ethyl substitution of the fluorophor.
In aggregation solution, with the increase of the poor water contents, the PL emission decreases significantly in the sPNNDPS23 (rrrrrr~59%) and sPNNDPS2 (rrrrrr~70%) due to the formation of H-aggregate in which extra energetic loss is conducted. By contrast, the PL spectra display that the emissive intensity decreases first as fw=0.1~0.5 and then intensifies later as fw=0.6~0.9. This might be resulted from the competition between the π-π interaction and RIR effect. Interestingly, the PL emissive intensity drops down significantly in the sPNNEPS, whereas the PL emissive intensity is almost unchanged in the aPNNEPS8 with the increase of the poor water contents. We suggest that because the aPNNEPS8 might contain both syndiotactic and isotactic configurations, the isotactic configurations having the ethyl group pointing out of the plane may prevent the formation of the π-stacking between the fluorophors.
The PL behavior in thin film is also explored for these stereoregular polymers. After slow cooling from melt, the crystalline sPNNDPS2 (rrrrrr~70%) thin film exhibits very strong emission in comparison with the thin film after quenching from melt, indicating the crystallization-induced emission enhancement. Although the iPNNDPS17 (mmmmmm~50%) is noncrystallizable as evidenced by differential scanning calorimetry (DSC) and polarized light microscope (PLM), the PL emissive intensity of the iPNNDPS17 (mmmmmm~50%) thin film is significantly stronger after slow cooling from melt than that after quenching from melt. We suggest that this might be attributed to the free volume effect varied with the thermal history associated with the steric hindrance. Notably, this enhanced PL emission in the iPNNDPS17 (mmmmmm~50%) thin film is extremely larger than that in the sPNNDPS23 (rrrrrr~59%) and aPNNDPS8, indicating the stereoregularity effect associated with the RIR effect. By contrast, this free volume effect is not significant in the PNNEPS thin film due to the flexible ethyl substitutions. As a result, the stereoregular polymers with different tacticities and regularities indeed exhibit distinct PL behavior in solution and thin film.
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