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. 2017 Feb 15;55(4):734-746.
doi: 10.1002/pola.28421. Epub 2016 Nov 21.

Fluorene-containing tetraphenylethylene molecules as lasing materials

C Orofino  1 , C Foucher  2 , F Farrell  1 , N J Findlay  1 , B Breig  1 , A L Kanibolotsky  1   3 , B Guilhabert  2 , F Vilela  4 , N Laurand  2 , M D Dawson  2 , P J Skabara  1
Affiliations

Fluorene-containing tetraphenylethylene molecules as lasing materials

C Orofino et al. J Polym Sci A Polym Chem. .

Abstract

A series of star-shaped oligofluorene molecules, each containing a TPE core, have been specifically designed and produced to show effective aggregation-induced emission (AIE). Each molecule differs either in the number of fluorene units within the arms (e.g., 1 or 4, compounds 4 and 5), or the terminal group positioned at the end of each arm (e.g., H, TMS, or TPA, compounds 4, 6, and 7). Although they are all poor emitters in solution phase they become efficient yellow-green luminogens in the condensed state. Their AIE properties were investigated in THF/H2O mixtures, with each molecule exhibiting a clear emission enhancement at specific water contents. An all-organic distributed feedback (DFB) laser was fabricated using compound 4 as the gain material and exhibited an average threshold energy fluence of 60 ± 6 μJ/cm2 and emission in the green region. Furthermore, piezofluorochromism studies on a thin film of this material displayed a linear dependence of the amplified spontaneous emission (ASE) peak position on applied pressure, indicating potential applications as lasing-based pressure sensors. © 2016 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 734-746.

Keywords: Synthesis; aggregation induced emission; oligomers; photophysics; piezofluorochromism.

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Figures

Scheme 1
Scheme 1
Synthesis of oligofluorene TPE analogs 4 and 5. Reagents and conditions: (a) Pd(PPh3)4, Ba(OH)2.8H2O, THF/H2O (10:1), reflux, 18 h.
Scheme 2
Scheme 2
Synthesis of TMS and TPA‐capped fluorene TPE analogues 6 and 7. Reagents and conditions: a) Pd(PPh3)4, Ba(OH)2.8H2O, THF/H2O (10:1), reflux, 18 h; b) Br2, NaOAc, THF, 17 h; c) 4‐(diphenylamino)phenyl boronic acid, Pd(PPh3)4, Ba(OH)2.8H2O, THF/H2O (10:1), reflux, 24 h and 4‐(diphenylamino)phenyl boronic acid, Pd(PPh3)4, Ba(OH)2.8H2O, THF/H2O (10:1), microwave, 2 h. * The yield of 28% is derived from the combination of both sets of conditions and further purification.
Figure 1
Figure 1
TPE‐cored star‐shaped systems 1–3 and trigonal oligofluorene series with truxene (T1‐4) and benzene (B1‐4) cores described in the literature.
Figure 2
Figure 2
General structures of compounds 4–7.
Figure 3
Figure 3
Normalized absorption and PL spectra of compounds 4–7 in dichloromethane. λ ex (compound 4) = 329 nm, λ ex (compound 5) = 372 nm, λ ex (compound 6) = 334 nm, λ ex (compound 7) = 368 nm. The peak values of the absorption/ emission spectra are marked.
Figure 4
Figure 4
Normalized absorption and PL spectra of compounds 4–7 in the solid state as films. λ ex (compound 4) = 330 nm, λ ex (compound 5) = 370 nm, λ ex (compound 6) = 349 nm, λ ex (compound 7) = 368 nm. The peak values of absorption/emission spectra and the onset of absorption are marked.
Figure 5
Figure 5
10 μM solutions of 4 (a) and 5 (b) in THF:H2O mixtures with increasing water fractions under UV (365 nm) illumination. From right to left 10, 20, 30, 40, 50, 60, 70, 80, and 90% water contents.
Figure 6
Figure 6
Emission spectra of 10−5 M solutions of 4 in THF:H2O mixtures with increasing water fraction. λ ex = 330 nm.
Figure 7
Figure 7
Emission spectra of 10−5 M solutions of 5 in THF:H2O mixtures with increasing water fractions. λ ex = 370 nm.
Figure 8
Figure 8
Intensity of the emission of compounds 4 and 5 in water:THF solutions relative to that in pure THF (I/I0) versus the water fraction (f w).
Figure 9
Figure 9
Spectrum (left) and power transfer function (right) of the laser.
Figure 10
Figure 10
Blue shifts of the ASE peaks obtained after applying different pressures on films of compound 4 with a hydraulic press.
Figure 11
Figure 11
Blue shifts of the ASE peaks obtained after applying different pressures on compound 4 films with a torque press.
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References

    1. Valeur B., Molecular Fluorescence: Principles and Applications; Weinheim, FRG: Wiley‐VCH Verlag GmbH, 2001, pp. 72–124.
    1. Skabara P. J., Arlin J. B., Geerts Y. H., Adv. Mater. 2013, 25, 1948–1954. - PubMed
    1. Kanibolotsky A. L., Perepichka I. F., Skabara P. J., Chem. Soc. Rev. 2010, 39, 2695–2728. - PubMed
    1. Vithanage D. A., Manousiadis P. P., Sajjad M. T., Rajbhandari S., Chun H., Orofino C., Cortizo‐Lacalle D., Kanibolotsky A. L., Faulkner G., Findlay N. J., O'Brien D. C., Skabara P. J., Samuel I. D. W., Turnbull G. A., Appl. Phys. Lett. 2016, 109, 013302.
    1. Sajjad M. T., Manousiadis P. P., Orofino C., Kanibolotsky A. L., Findlay N. J., Rajbhandari S., Vithanage D. A., Chun H., Faulkner G., O'Brien D. C., Skabara P. J., Turnbull G. A., Samuel I. D. W., Appl. Phys. Lett. submitted.