Dramatic femtosecond nonlinear absorption at a strongly coupled porphyrin-graphene nanoconjugate
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Edge-functionalization of graphene is emerging as a powerful chemical method for the construction of π-delocalized highly-planar graphene nanoconjugates that are not accessible through surface-supported syntheses. Herein, a graphene-porphyrin nanoconjugate via a robust pyrazine (pz) linkage has been obtained by condensing 2,3-diamino-5,10,15,20-tetraphenylporphyrin (DA-TPP) with ortho-quinone (o-quinone) moieties at edge sites of graphene oxide (GO). The as-prepared GO-pz-TPP exhibits an intense absorption extending from 375 to 900 nm and a high quenching yield (98%) of fluorescence, indicating a strong electronic coupling effect between GO and TPP units. GO-pz-TPP displays strong nonlinear optical (NLO) absorption and giant NLO coefficients with 800 and 1,030 nm fs laser, in sharp contrast to traditional graphene-porphyrin nanohybrids only NLO-active towards ns laser. Such a dramatic NLO performance towards femtosecond pulsed laser has not been achieved in any carbon-chromophores nanohybridized materials to date. This work validates the π-extended edge-functionalization strategy as a means to tune the NLO properties of graphene, thereby providing a new paradigm for the assembly of versatile optoelectronic materials.
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Dramatic femtosecond nonlinear absorption at a strongly coupled porphyrin-graphene nanoconjugate
)
Abstract
Edge-functionalization of graphene is emerging as a powerful chemical method for the construction of π-delocalized highly-planar graphene nanoconjugates that are not accessible through surface-supported syntheses. Herein, a graphene-porphyrin nanoconjugate via a robust pyrazine (pz) linkage has been obtained by condensing 2,3-diamino-5,10,15,20-tetraphenylporphyrin (DA-TPP) with ortho-quinone (o-quinone) moieties at edge sites of graphene oxide (GO). The as-prepared GO-pz-TPP exhibits an intense absorption extending from 375 to 900 nm and a high quenching yield (98%) of fluorescence, indicating a strong electronic coupling effect between GO and TPP units. GO-pz-TPP displays strong nonlinear optical (NLO) absorption and giant NLO coefficients with 800 and 1,030 nm fs laser, in sharp contrast to traditional graphene-porphyrin nanohybrids only NLO-active towards ns laser. Such a dramatic NLO performance towards femtosecond pulsed laser has not been achieved in any carbon-chromophores nanohybridized materials to date. This work validates the π-extended edge-functionalization strategy as a means to tune the NLO properties of graphene, thereby providing a new paradigm for the assembly of versatile optoelectronic materials.
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Acknowledgements
Financial support from the National Natural Science Foundation of China (No. 51432006), the Ministry of Science and Technology of China for the International Science Linkages Program (No. 2011DFG52970), the Ministry of Education of China for the Changjiang Innovation Research Team (No. IRT14R23), the Ministry of Education and the State Administration of Foreign Experts Affairs for the 111 Project (No. B13025), and the Innovation Program of Shanghai Municipal Education Commission are gratefully acknowledged. M.G.H thanks the Australian Research Council (No. DP170100411) for support.
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