Enhanced non-linear optical properties of porphyrin-based polymers covalently functionalized with graphite phase carbon nitride

用石墨相氮化碳共价功能化的卟啉基聚合物的非线性光学性质得到增强

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Abstract

In our work, a flurry of original porphyrin-based polymers covalently functionalized g-C(3)N(4) nanohybrids were constructed and nominated as PPorx-g-C(3)N(4) (x = 1, 2 and 3) through click chemistry between porphyrin-based polymers with alkyne end-groups [(PPorx-C≡CH (x = 1, 2 and 3)] and azide-functionalized graphitic carbon nitride (g-C(3)N(4)-N(3)). Due to the photoinduced electron transfer (PET) between porphyrin-based polymers [PPorx (x = 1, 2 and 3)] group and graphite phase carbon nitride (g-C(3)N(4)) group in PPorx-g-C(3)N(4) nanohybrids, the PPorx-g-C(3)N(4) nanohybrids exhibited better non-linear optical (NLO) performance than the corresponding PPorx-C≡CH and g-C(3)N(4)-N(3). It found that the imaginary third-order susceptibility (Im [χ((3))]) value of the nanohybrids with different molecular weight (MW) of the pPorx group in the nanohybrids ranged from 2.5×10(3) to 7.0 × 10(3) g mol(-1) was disparate. Quite interestingly, the Im [χ((3))] value of the nanohybrid with a pPorx group's MW of 4.2 × 10(3) g mol(-1) (PPor2-g-C(3)N(4)) was 1.47 × 10(-10) esu, which exhibited the best NLO performance in methyl methacrylate (MMA) of all nanohybrids. The PPorx-g-C(3)N(4) was dispersed in polymethyl methacrylate (PMMA) to prepare the composites PPorx-g-C(3)N(4)/PMMA since PMMA was widely used as an alternative to glass. PPor2-g-C(3)N(4)/PMMA showed the excellent NLO performance of all nanohybrids with the Im [χ((3))] value of 2.36 × 10(-10) esu, limiting threshold of 1.71 J/cm(2), minimum transmittance of 8% and dynamic range of 1.09 in PMMA, respectively. It suggested that PPorx-g-C(3)N(4) nanohybrids were potential outstanding NLO materials.

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