Search

Two series of quadrupolar diphenylamino-endcapped oligofluorenes, PhN-OF(n)-NPh (n=2-5) and PhN-OF(n)-TAZ-OF(n)-NPh (n=1-4), which have an electron-withdrawing 1,2,4-triazole (TAZ) moiety as central core, with D-π-A-π-D structural motif (D=donor, A=acceptor), have been synthesized by palladium-catalyzed Suzuki cross-coupling of 9,9-dibutyl-7-(diphenylamino)-2-fluorenylboronic acid and the corresponding (1,2,4-triazole-based) aryl halide as key step. On pumping with infrared femtosecond lasers, these oligomers showed very strong multiphoton-excited blue photoluminescence. These D-π-D and D-π-A-π-D quadrupolar oligofluorenes exhibit superior three-photon absorption properties compared to the respective D-π-A counterparts with a highest three-photon absorption cross-section (σ(3)) of up to 2.72×10(-77) cm(6) s(2) . Despite the comparable linear and multiphoton absorption properties of the two types of quadrupolar oligomers PhN-OF(n)-NPh and PhN-OF(n)-TAZ-OF(n)-NPh, only the former exhibit remarkably intense and highly efficient multiphoton-excited frequency-upconverted deep blue lasing, which gives rise to record high lasing efficiency of 0.097% and very narrow of full width at half-maximum of the lasing spectra. Our findings suggest that quadrupolar-type molecules/oligomers are superior for multiphoton excited frequency upconverted lasing to their dipolar counterparts and also provide important guidelines to design highly efficient three-photon absorption molecules for photoluminescence and lasing applications.

A novel series of diphenyl-amino- and 1,2,4-triazole-end-capped, fluorene-based, π-conjugated oligomers that includes extended oligofluorenes and oligothienylfluorenes has been synthesized by means of the palladium-catalyzed Suzuki cross-coupling of 9,9-dibutyl-7-(diphenylamino)-2-fluorenyl-boronic acid and the corresponding 1,2,4,-triazole-based aryl halide as a key step. It was demonstrated that efficient two- and three-photon excited photoluminescence and lasing in the blue region are obtained by pumping near-infrared femtosecond lasers on these materials. Although the absorption and emission maxima of the highly fluorescent and extended oligofluorenes reach a saturation limit, there exists an effective conjugation length for an optimum three-photon absorption cross section in the homologous oligofluorene series. On the other hand, the multiphoton excited emission spectrum and lasing wavelength can easily be modified or tuned by an incorporation of thienyl unit(s) into the fluorene-based π-conjugated core with which exceptionally large three-photon absorption cross sections up to 3.59× 10 ―77 cm 6 s 2 in the femtosecond regime have been obtained, thereby highlighting the potential of this series of photonic materials. The optimized full width at half-maximum of the cavity-less three-photon upconverted blue lasing spectra are sharply narrowed to approximately 6 nm with an efficiency of up to 0.013 %.

Star-shaped ladder-type ter(p-phenylene)s exhibit remarkably efficient multiphoton absorption properties with 2PA cross-section up to 2579 GM at 700 nm and 3PA cross-section up to 3.35 × 10(-76) cm(6) s(2) in the femtosecond regime for a blue-emissive molecule despite having such a short π-conjugated framework.

Remarkably strong multiphoton, from two- to five-photon, upconverted violet fluorescence is first observed on a calix[4]arene-based multi-dipolar assembly which is strongly enhanced as compared to that of the corresponding dipolar counterparts.

A novel homologues series of diphenylamino and 1,2,4-triazole endcapped pi-conjugated oligofluorenes has been synthesized using palladium-catalyzed Suzuki cross-coupling of 9,9-dibutyl-7-(diphenylamino)-2-fluorenylboronic acid, and 1,2,4,-triazole-substituted oligofluorenyl halide was used as a key step. Efficient two- and three-photon excited photoluminescence and lasing were obtained by pumping with near-infrared femto-second lasers. The three-photon absorption cross-section enhances significantly up to 2.48 x 10(-78) cm(6) s(2) in the femtosecond regime with the length of the conjugation system. The emission is in the deep blue region and the best full width half-maximum (fwhm) of the three-photon lasing is narrower than 6 nm which is the narrowest ever reported. It was also shown that the nonlinear optics (NLO) effect increased parabolically with the conjugation length but without changing the emission wavelength. This demonstrates that varying the conjugation length is a very effective way to tailor an OF-based NLO device for deep blue application. Our findings open a new avenue to design highly efficient multiphoton absorption molecules for photoluminescence and lasing as well as provide a novel series of organic molecules that can be used in NLO applications and fundamental study.