Liang Chen, Cui Xu, Dong Wenyue, Qin Jieming, Duan Qian
School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun, China.
Engineering Research Center of Optoelectronic Functional Materials, Ministry of Education, Changchun, China.
Front Chem. 2022 Dec 15;10:1102666. doi: 10.3389/fchem.2022.1102666. eCollection 2022.
In our work, a flurry of original porphyrin-based polymers covalently functionalized g-CN nanohybrids were constructed and nominated as PPorx-g-CN (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-CN-N). Due to the photoinduced electron transfer (PET) between porphyrin-based polymers [PPorx (x = 1, 2 and 3)] group and graphite phase carbon nitride (g-CN) group in PPorx-g-CN nanohybrids, the PPorx-g-CN nanohybrids exhibited better non-linear optical (NLO) performance than the corresponding PPorx-C≡CH and g-CN-N. It found that the imaginary third-order susceptibility ( [χ]) value of the nanohybrids with different molecular weight (MW) of the Porx group in the nanohybrids ranged from 2.5×10 to 7.0 × 10 g mol was disparate. Quite interestingly, the [χ] value of the nanohybrid with a Porx group's MW of 4.2 × 10 g mol (PPor2-g-CN) was 1.47 × 10 esu, which exhibited the best NLO performance in methyl methacrylate (MMA) of all nanohybrids. The PPorx-g-CN was dispersed in polymethyl methacrylate (PMMA) to prepare the composites PPorx-g-CN/PMMA since PMMA was widely used as an alternative to glass. PPor2-g-CN/PMMA showed the excellent NLO performance of all nanohybrids with the [χ] value of 2.36 × 10 esu, limiting threshold of 1.71 J/cm, minimum transmittance of 8% and dynamic range of 1.09 in PMMA, respectively. It suggested that PPorx-g-CN nanohybrids were potential outstanding NLO materials.
在我们的工作中，通过末端带有炔基的卟啉基聚合物[PPorx-C≡CH（x = 1、2和3）]与叠氮基官能化的石墨相氮化碳（g-CN-N）之间的点击化学，构建了一系列共价功能化的基于卟啉的聚合物修饰的g-CN纳米杂化物，并将其命名为PPorx-g-CN（x = 1、2和3）。由于PPorx-g-CN纳米杂化物中基于卟啉的聚合物[PPorx（x = 1、2和3）]基团与石墨相氮化碳（g-CN）基团之间的光致电子转移（PET），PPorx-g-CN纳米杂化物表现出比相应的PPorx-C≡CH和g-CN-N更好的非线性光学（NLO）性能。研究发现，纳米杂化物中具有不同分子量（MW）的Porx基团的纳米杂化物的虚部三阶极化率（[χ]）值在2.5×10至7.0×10 g·mol范围内各不相同。非常有趣的是，Porx基团MW为4.2×10 g·mol的纳米杂化物（PPor2-g-CN）的[χ]值为1.47×10 esu，在所有纳米杂化物中其在甲基丙烯酸甲酯（MMA）中表现出最佳的NLO性能。由于聚甲基丙烯酸甲酯（PMMA）被广泛用作玻璃的替代品，因此将PPorx-g-CN分散在聚甲基丙烯酸甲酯（PMMA）中以制备复合材料PPorx-g-CN/PMMA。PPor2-g-CN/PMMA在所有纳米杂化物中表现出优异的NLO性能，其[χ]值为2.36×10 esu，在PMMA中的限制阈值为1.71 J/cm，最小透过率为8%，动态范围为1.09。这表明PPorx-g-CN纳米杂化物是潜在的优异NLO材料。
