Citation: Li-Wen Hu, Liang Li, Yong Yang, Ting Guo, Yu-Hao Zhang, Wei Yang, Yong Cao. Green-emitting Polyfluorenes Containing Hexylthiophen-dibenzothiophene-S, S-dioxide Unit with Large Two-photon Absorption Cross Section[J]. Chinese Journal of Polymer Science, ;2018, 36(4): 546-554. doi: 10.1007/s10118-018-2017-y shu

Green-emitting Polyfluorenes Containing Hexylthiophen-dibenzothiophene-S, S-dioxide Unit with Large Two-photon Absorption Cross Section

Institute of Polymer Optoelectronic Materials and Devices, State Key Laboratory of Luminescent Materials and Devices, South China University of Technology, Guangzhou 510640, China

Corresponding author: Ting Guo, mstguo@scut.edu.cn Wei Yang, pswyang@scut.edu.cn
Received Date: 28 June 2017
Accepted Date: 5 August 2017
Available Online: 16 November 2017

Green light-emitting polyfluorenes containing 3, 7-bis(4-hexylthiophen-2-yl)dibenzo[b, d]thiophene 5, 5-dioxide (DHTSO) unit were synthesized. All the resulted polymers show high thermal stability with the decomposition temperatures (T_d) over 420℃ and the glass transition temperatures (T_g) over 75℃. The polymers exhibit the enhanced highest occupied molecular orbital (HOMO) energy levels and the depressed lowest unoccupied molecular orbital (LUMO) energy levels with the increase of DHTSO unit in polymers. The photoluminescence (PL) spectra of the polymers show positive solvatochromism in solution with the variation of solution polarities, indicating remarkable intramolecular charge transfer (ICT) effect in the polymers containing DHTSO moiety. The fluorescence quantum yields (φ_PL) are in the range of 34%-67% for PF-DHTSOs in film. All polymers possess two photon absorption (TPA) properties, and the TPA cross sections (δ₂) are enhanced with increasing DHTSO unit in polymers. The highest δ₂ is 2392 GM for PF-DHTSO15 in chloroform solution upon 740 nm excitation. The device of PF-DHTSO15 shows green emission with the Commission Internationale de L'. Eclairage (CIE) coordinates of (0.26, 0.59), and the maximum luminous efficiency (LE_max) of 10.8 cd·A^-1 with the configuration of ITO/PEDOT:PSS/EL/CsF/Al. These results indicate that introducing DHTSO unit into polyfluorene backbone could be a promising molecular design strategy for TPA and effective green-light emission.
- DHTSO,
- Polyfluorene,
- TPA,
- Green emission,
- PLED
1. [1]
  Xie L. H., Yin C. R., Lai W. Y., Fan Q. L., Huang W.. Polyfluorene-based semiconductors combined with various periodic table elements for organic electronics[J]. Prog. Polym. Sci., 2012,37(9):1192-1264. doi: 10.1016/j.progpolymsci.2012.02.003
2. [2]
  Zhu M. R., Yang C. L.. Blue fluorescent emitters:design tactics and applications in organic light-emitting diodes[J]. Chem. Soc. Rev., 2013,42:4963-4976. doi: 10.1039/c3cs35440g
3. [3]
  Jiang G. X., Bian C. L., Ding J. Q., Wang L. X.. Synthesis and characterization of blue light-emitting poly(aryl ether)s containing pyrimidine-incorporated oligofluorene pendants with bipolar feature[J]. Chinese J. Polym. Sci., 2013,31(5):787-797. doi: 10.1007/s10118-013-1279-7
4. [4]
  Wu W. B., Tang R. L., Li Q. Q., Li Z.. Functional hyperbranched polymers with advanced optical, electrical and magnetic properties[J]. Chem. Soc. Rev., 2015,44:3997-4022. doi: 10.1039/C4CS00224E
5. [5]
  Chen S. H., Su A. C., Su C. H., Chen S. A.. Crystalline forms and emission behavior of poly(9, 9-di-n-octyl-2, 7-fluorene)[J]. Macromolecules, 2005,38(2):379-385. doi: 10.1021/ma048162t
6. [6]
  Hu S. J., Zhu M. R., Zou Q. H., Wu H. B., Yang C. L., Wong W. Y., Yang W., Peng J. B., Cao Y.. Efficient hybrid white polymer light-emitting devices with electroluminescence covered the entire visible range and reduced efficiency roll-off[J]. Appl. Phys. Lett., 2012,100(6)063304. doi: 10.1063/1.3682526
7. [7]
  Schelkle K. M., Bender M., Jeltsch K., Buckup T., Mîllen K., Hamburger M.. Light-induced solubility modulation of polyfluorene to enhance the performance of OLEDs[J]. Angew. Chem. Int. Ed., 2015,54(48):14545-14548. doi: 10.1002/anie.201505141
8. [8]
  Liu W., Sun M. L., Liu Q., He B. L., Ge H. L., Sun M., Zhang Q. J., Wang W.. An electrochemically prepared sky-blue light emitting ether functionalized polyfluorene as chemosensor for metal ions[J]. Chinese J. Polym. Sci., 2013,31(11):1579-1589. doi: 10.1007/s10118-013-1352-2
9. [9]
  Chen L., Li P. C., Tong H., Xie Z. Y., Wang L. X., Jing X. B., Wang F. S.. White electroluminescent single-polymer achieved by incorporating three polyfluorene blue arms into a star-shaped orange core[J]. J. Polym. Sci., Part A:Polym. Chem., 2012,50(14):2854-2862. doi: 10.1002/pola.26061
10. [10]
  Xiao H. P., Yu L., Li Y. H., Yang W., Zhang B., Yang W., Wu H. B., Cao Y.. Novel green light-emitting polyfluorenes containing dibenzothiophene-S, S-dioxide-arylamine derivatives[J]. Polymer, 2012,53(14):2873-2883. doi: 10.1016/j.polymer.2012.05.011
11. [11]
  Li J. Y., Ziegler A., Wegner G.. Substituent effect to prevent autoxidation and improve spectral stability in blue light-emitting polyfluorenes[J]. Chem. Eur. J., 2005,11(15):4450-4457. doi: 10.1002/chem.v11:15
12. [12]
  Kim G., Basarir F., Yoon T. H.. Synthesis and characterization of poly(triphenyl-amine)s with electron-withdrawing trifluoromethyl side groups for emissive and hole-transporting layer[J]. Synth. Met., 2011,161(19-20):2092-2096. doi: 10.1016/j.synthmet.2011.07.026
13. [13]
  Purc A., Sobczyk K., Sakagam Y., Ando A., Kamada K., Gryko D. T.. Strategy towards large two-photon absorption cross-sections for diketopyrrolopyrroles[J]. J. Mater. Chem. C, 2015,3(4):742-749. doi: 10.1039/C4TC02375G
14. [14]
  Goswami S., Winkel R. W., Schanze K. S.. Photophysics and nonlinear absorption of Gold(I) and Platinum(Ⅱ) donor-acceptor-donor chromophores[J]. Inorg. Chem., 2015,54(20):10007-10014. doi: 10.1021/acs.inorgchem.5b01767
15. [15]
  Hu W. B., He T. C., Jiang R. C., Yin J., Li L., Lu X. M., Zhao H., Zhang L., Huang L., Sun H. D., Huang W., Fan Q. L.. Inner salt-shaped small molecular photosensitizer with extremely enhanced two-photon absorption for mitochondrial-targeted photodynamic therapy[J]. Chem. Commun., 2017,53(10):1680-1683. doi: 10.1039/C6CC09473B
16. [16]
  Zhou W. Y., Jin F., Huang X. B., Duan X. M., Zhan X. W.. A low-bandgap conjugated copolymer based on porphyrin and dithienocoronene diimide with strong two-photon absorption[J]. Macromolecules, 2012,45(19):7823-7828. doi: 10.1021/ma3015257
17. [17]
  Huang X. B., Shi Q. Q., Chen W. Q., Zhu C. L., Zhou W. Y., Zhao Z., Duan X. M., Zhan X. W.. Low-bandgap conjugated donor-acceptor copolymers based on porphyrin with strong two-photon absorption[J]. Macromolecules, 2010,43(23):9620-9626. doi: 10.1021/ma102275h
18. [18]
  Mariz I. F. A., Maçôas E. M. S., Martinho J. M. G., Zou L., Zhou P. C., Chen X. G., Qin J. G.. Molecular architecture effects in two-photon absorption:from octupolar molecules to polymers and hybrid polymer nanoparticles based on 1, 3, 5-triazine[J]. J. Mater. Chem. B, 2013,1(16):2169-2177. doi: 10.1039/c3tb20107d
19. [19]
  Zhou P. C., Zhong C., Chen X. G., Qin J. G., Mariz I. E.. Maçôas E. New kind of hyperbranched conjugated polymers containing alkyl-modified 2, 4, 6-tris(thiophen-2-yl)-1, 3, 5-triazine unit for enhancing two-photon absorption[J]. Macromolecules, 2014,47(19):6679-6686. doi: 10.1021/ma500914v
20. [20]
  King S. M., Perepichka I. I., Perepichka I. F., Dias F. B., Bryce M. R., Monkman A. P.. Exploiting a dual-fluorescence process in fluorene-dibenzothiophene-S, S-dioxide co-polymers to give efficient single polymer LEDs with broadened emission[J]. Adv. Funct. Mater., 2009,19(4):586-591. doi: 10.1002/adfm.v19:4
21. [21]
  He, Xu, Yang, Cai, Chen, Ying, Yang, C, Y. Dibenzothiophene-S, S-dioxide based medium-band-gap polymers for efficient bulk heterojunction solar cells[J]. Org. Electron, 2014,15(11):2950-2958. doi: 10.1016/j.orgel.2014.08.026
22. [22]
  Perepichka I. I., Perepichka I. F., Bryce M. R., Pålsson L.O.. Dibenzothiophene-S, S-dioxide-fluorene co-oligomers. Stable, highly-efficientblue emitters with improved electron affinity[J]. Chem. Commun., 2005:3397-3399.
23. [23]
  Hsu C. Y., Hsieh M. T., Tsai M. K., Li Y. J., Huang C. J., Su Y. K., Whang T. J.. Fluorescent oligomers of dibenzothiophene-S, S-dioxide derivatives:the interplay of crystal conformations and photo-physical properties[J]. Tetrahedron, 2012,68(27-28):5481-5491. doi: 10.1016/j.tet.2012.04.085
24. [24]
  Gsanger M., Oh J. H., Konemann M., Hoffken H. W., Krause A. M., Bao Z., Wurthner F. A.. Crystal-engineered hydrogen-bonded octachloroperylene diimide with a twisted core:an n-channel organic semiconductor[J]. Angew. Chem. Int. Ed., 2010,49(4):740-743. doi: 10.1002/anie.200904215
25. [25]
  Jiu Y. D., Wang J. Y., Liu C. F., Lai W. Y., Zhao L. L., Li C. L., Jiang Y., Xu W. D., Zhang X. W., Huang W.. White electroluminescence with simultaneous three-color emission from a four-armed star-shaped single-polymer system[J]. Chin. J. Chem., 2015,33(8):873-880. doi: 10.1002/cjoc.v33.8
26. [26]
  Jin F., Cai Z. B., Huang J. Q., Li S. L., Tian Y. P.. Investigation of two-photon absorption properties in new A-D-A compounds emitting blue and yellow fluorescence[J]. J. Mol. Struct., 2015,1093:33-38. doi: 10.1016/j.molstruc.2015.03.036
27. [27]
  He R. F., Hu S. J., Liu J., Yu L., Zhang B., Li N., Yang W., Wu H. B., Peng J. B.. Bipolar blue-emitting poly(N-9'-heptadecanyl-carbazole-2, 7-diyl-co-dibenzo-thiophene-S, S-dio-xide-3, 7-diyl)s[J]. J. Mater. Chem., 2012,22(8):3440-3446. doi: 10.1039/c2jm14926e
28. [28]
  Wang M., Li Y., Xie Z. Y., Wang L. X.. Polyfluorenes containing pyrazine units:Synthesis, photophysics and electroluminescence[J]. Sci. China Chem., 2011,54(4):656-665. doi: 10.1007/s11426-011-4238-6
29. [29]
  Wang S. C., Xu S. S., Wang Y. M., Tian X. H., Zhang Y. J., Wang C. K., Wu J. Y., Yang J. X., Ti an, Y. P.. Synthesis, crystals of centrosymmetric triphenylamine chromophores bearing prodigious two-photon absorption cross-section and biological imaging[J]. Spectrochim. Acta A, 2017,173:871-879. doi: 10.1016/j.saa.2016.10.059
30. [30]
  Makarov N. S., Drobizhev M., Rebane A.. Two-photon absorption standards in the 550-, 1600 nm excitation wavelength range[J]. Opt. Express, 2008,16(6):4029-4047. doi: 10.1364/OE.16.004029
31. [31]
  Gao Y. T., Qu Y., Jiang T., Zhang H., He N. N., Li B., Wu J. C., Hua J. L.. Alkyl-triphenylamine end-capped triazines with AIE and large two-photon absorption cross-sections for bioimaging[J]. J. Mater. Chem. C, 2014,2(31):6353-6361. doi: 10.1039/C4TC00910J
32. [32]
  Druzhinin S. K., Galievsky V. A., Demeter A., Kovalenko S. A., Senyushkina T., Dubbaka S. R., Knoche P., Mayer P., Grosse C., Stalke D.. Two-state intramolecular charge transfer (ICT) with 3, 5-dimethyl-4-(dimethylamino)-benzo-nitrile (MMD) and its meta-isomer mMMD. Ground state amino twist not essential for ICT[J]. J. Phys. Chem. A, 2015,119(48):11820-11836.
33. [33]
  Priya J., Samarendra P. S.. Dependence of the structure and electronic properties of D-A-D based molecules on the D/A ratio and the strength of the acceptor moiety[J]. J. Phys. Chem. C, 2015,119(27):14890-14899. doi: 10.1021/acs.jpcc.5b02404
34. [34]
  Lan S. C., Raghunath P., Lu Y. H., Wang Y. C., Lin S. W., Liu C. M., Jiang J. M., Lin M. C., Wei K. H.. Symmetry and coplanarity of organic molecules affect their packing and photovoltaic properties in solution-processed solar cells[J]. ACS Appl. Mater. Interfaces, 2014,6(12):9298-9306. doi: 10.1021/am501659u
35. [35]
  Li Q. Q., Zhong C., Huang J., Huang Z. L., Pei Z. G., Liu J., Qin J. G., Li Z.. Conjugated polymers with pyrrole as the conjugated bridge:synthesis, characterization, and two-photon absorption properties[J]. J. Phys. Chem. B, 2011,115(27):8679-8685. doi: 10.1021/jp2015484
36. [36]
  Frisch, M. J. ; Trucks, G. W. ; Schlegel, H. B. ; Scuseria, G. E. ; Robb, M. A. ; Cheeseman, J. R. ; Scalmani, G. ; Barone, V. ; Mennucci, B. ; Petersson, G. A. ; Nakatsuji, H. ; Caricato, M. ; Li, X. ; Hratchian, H. P. ; Izmaylov, A. F. ; Bloino, J. ; Zheng, G. ; Sonnenberg, J. L. ; Hada, M. ; Ehara, M. ; Toyota, K. ; Fukuda, R. ; Hasegawa, J. ; Ishida, M. ; Nakajima, T. ; Honda, Y. ; Kitao, O. ; Nakai, H. ; Vreven, T. ; Montgomery, J. A. ; Peralta, J. E. ; Ogliaro, F. ; Bearpark, M. ; Heyd, J. J. ; Brothers, E. ; Kudin, K. N. ; Staroverov, V. N. ; Kobayashi, R. ; Normand, J. ; Raghavachari, K. ; Rendell, A. ; Burant, J. C. ; Iyengar, S. S. ; Tomasi, J. ; Cossi, M. ; Rega, N. ; Millam, J. M. ; Klene, M. ; Knox, J. E. ; Cross, J. B. ; Bakken, V. ; Adamo, C. ; Jaramillo, J. ; Gomperts, R. ; Stratmann, R. E. ; Yazyev, O. ; Austin, A. J. ; Cammi, R. ; Pomelli, C. ; Ochterski, J. W. ; Martin, R. L. ; Morokuma, K. ; Zakrzewski, V. G. ; Voth, G. A. ; Salvador, P. ; Dannenberg, J. J. ; Dapprich, S. ; Daniels, A. D. ; Farkas, Ö. ; Foresman, J. B. ; Ortiz, J. V. ; Cioslowski, J. ; Fox, D. J. Gaussian 09, Revision D. 01; Gaussian, Inc. : Wallingford, CT, 2009.
37. [37]
  Hu L. W., Yang Y., Xu J., Liang J. F., Guo T., Zhang B., Yang W., Cao Y.. Blue light-emitting polymers containing fluorine based benzothiophene-S, S-dioxide derivatives J[J]. Mater. Chem. C, 2016,4(6):1305-1312. doi: 10.1039/C5TC03197D
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