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Highly efficient and stable solid-state luminescent nanohybrids: Precise architecture and enhancement mechanism

  • Ya Kun Zhu (a1), Shan Yi Guang (a2), Xin Yan Su (a3), Hong Yao Xu (a3) and Xiang Yang Liu (a4)...


The organic light-emitting (OLE) materials have attracted great interest due to their potential applications in sensors, biodetectors and OLE devices. However, highly efficient emission from organic solids is still a great challenge because of the aggregation-caused quenching effect. In this article, a three-dimensional (3D) organic-inorganic hybrid nanoparticle, based on polyhedral oligomeric silsesquioxane (POSS), was precisely fabricated via click chemistry with high yield, and its structure was characterized by Fourier transform infrared spectroscopy, 1H, and 29Si nuclear magnetic resonance spectroscopies, and Matrix-Assisted Laser Desorption Ionization Time-of-Flight Mass Spectrometry, respectively. The resultant 3D organic-inorganic nanohybrid showed significantly enhanced emission in solid film (Φfilm 80%) with a slight red-shift as compared with its organic counterpart, (Φfilm 14%), which exhibits a large red-shift in solid film, due to the deaggregation effect of POSS. Simultaneously, the resultant nanohybrid also exhibited good film formability, excellent spectrum and thermal stability (>250 °C) due to the introduction of POSS.


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1.Pu, K.Y. and Liu, B.: Conjugated polyelectrolytes as light-up macromolecular probes for heparin sensing. Adv. Funct. Mater. 19, 277 (2009).
2.Lott, J., Ryan, C., Valle, B., Johnson, J.R. III, Schiraldi, D.A., Shan, J., Singer, K.D., and Weder, C.: Two-photon 3D optical data storage via aggregate switching of excimer-forming dyes. Adv. Mater. 23, 2425 (2011).
3.Dou, L.T., You, J.B., Yang, J., Chen, C.C., He, Y.J., Murase, S., Moriarty, T., Emery, K., Li, G., and Yang, Y.: Tandem polymer solar cells featuring a spectrally matched low-bandgap polymer. Nat. Photonics 6, 180 (2012).
4.Feast, W.J. and Kilbinger, A.F.M.: Solution processable alternating oligothiophene-PEO-block-co-polymers: Synthesis and evidence for solvent dependent aggregation. J. Mater. Chem. 10, 1777 (2000).
5.Sun, X.B., Xu, X.J., Qiu, W.F., Yu, G., Zhang, H.J., Gao, X.K., Chen, S.Y., Song, Y.L., and Liu, Y.Q.: A non-planar pentaphenylbenzene functionalized benzo [2,1,3] thiadiazole derivative as a novel red molecular emitter for non-doped organic light-emitting diodes. J. Mater. Chem. 18, 2709 (2008).
6.Lukyanov, A., Malafeev, A., Ivanov, V., Chen, H.L., Kremer, K., and Andrienko, D.: Solvated poly-(phenylene vinylene) derivatives: Conformational structure and aggregation behavior. J. Mater. Chem. 20, 10475 (2010).
7.Wang, H.T., Bai, F.Q., Liu, H.M., Bai, B.L., Ran, X., Qu, S.N., Shi, J.H., Xie, D.J., Li, H.Y., Li, M., and Zhang, H.X.: Experimental and theoretical study on molecular aggregation and its effect on the photo-physical properties of the mesogenic bi-1,3,4-thiadiazole derivative. Phys. Chem. Chem. Phys. 13, 9697 (2011).
8.Romero-Nieto, C., Merino, S., Rodriguez-Lopez, J., and Baumgartner, T.: Dendrimeric oligo(phenylenevinylene)-extended dithieno[3,2-b:2′,3′-d]phospholes: Synthesis, self-organization, and optical properties. Chem. Eur. J. 15, 4135 (2009).
9.You, J., Li, G.Y., Wang, R.J., Nie, Q.P., Wang, Z.G., and Li, J.Y.: Pyrene-cored dendrimer with carbazole derivatives as dendrons: Synthesis, properties and application in white light-emitting diode. Phys. Chem. Chem. Phys. 13, 17825 (2011).
10.Lekha, P.K. and Prasad, E.: Tunable emission of static excimer in a pyrene-modified polyamidoamine dendrimer aggregate through positive solvatochromism. Chem. Eur. J. 17, 8609 (2011).
11.Ma, J.F., Zhang, L.P., Yang, J., Liu, Y.Y., and Wei, G.H.: 1D, 2D, and 3D metal-organic frameworks based on bis(imidazole) ligands and polycarboxylates: Syntheses, structures, and photoluminescent properties. Cryst. Growth Des. 9, 4660 (2009).
12.Trastoy, B., Perez-Ojeda, M.E., Sastre, R., and Chiara, J.L.: Octakis(3-azidopropyl)octasilsesquioxane: A versatile nanobuilding block for the efficient preparation of highly functionalized cube-octameric polyhedral oligosilsesquioxane frameworks through click assembly. Chem. Eur. J. 16, 3833 (2010).
13.You, H.P., Liu, K., Zheng, Y.H., Jia, G., Song, Y.H., Huang, Y.J., Yang, M., Jia, J.J., Guo, N., and Zhang, H.J.: Facile and rapid fabrication of metal-organic framework nanobelts and color-tunable photoluminescence properties. J. Mater. Chem. 20, 3272 (2010).
14.Mintzer, M.A. and Grinstaff, M.W.: Biomedical applications of dendrimers: A tutorial. Chem. Soc. Rev. 40, 173 (2011).
15.Yang, X.H., Froehlich, J.D., Chae, H.S., Li, S., Mochizuki, A., and Jabbour, G.E.: Novel orange-red light-emitting polymers with cyclometaled iridium complex grafted in alkyl chain. Adv. Funct. Mater. 19, 2623 (2009).
16.Tanaka, K. and Chujo, Y.: Advanced functional materials based on polyhedral oligomeric silsesquioxane (POSS). J. Mater. Chem. 22, 1733 (2012).
17.Wang, F.K., Lu, X.H., and He, C.B.: Some recent developments of polyhedral oligomeric silsesquioxane (POSS)- based polymeric materials. J. Mater. Chem. 21, 2775 (2011).
18.Yan, Z.Q., Xu, H.Y., Guang, S.Y., Zhao, X., Fan, W., and Liu, X.Y.: A convenient organic–inorganic hybrid approach toward highly stable squaraine dyes with reduced H-aggregation. Adv. Funct. Mater. 22, 345 (2012).
19.Wang, X., Guang, S.Y., Xu, H.Y., Su, X.Y., Yang, J.Y., Song, Y.L., Lin, N.B., and Liu, X.Y.: Thermally stable oxadiazole-containing polyacetylenes: Relationship between molecular structure and nonlinear optical properties. J. Mater. Chem. 18, 4204 (2008).
20.Chu, Y.L., Cheng, C.C., Chen, Y.P., Yen, Y.C., and Chang, F.C.: A new supramolecular POSS electroluminescent material. J. Mater. Chem. 22, 9285 (2012).
21.Wu, Y.C. and Kuo, S.W.: Self-assembly supramolecular structure through complementary multiple hydrogen bonding of heteronucleobase-multifunctionalized polyhedral oligomeric silsesquioxane (POSS) complexes. J. Mater. Chem. 22, 2982 (2012).
22.Yang, B.H., Xu, H.Y., Yang, Z.Z., and Zhang, C.: Controllable preparation of ultra-low-dielectric nanoporous silica via inorganic-organic hybrid templates. J. Mater. Chem. 20, 2469 (2010).
23.Su, X.Y., Guang, S.Y., Li, C.W., Xu, H.Y., Liu, X.Y., Wang, X., and Song, Y.L.: Molecular hybrid optical limiting materials from polyhedral oligomer silsesquioxane: Preparation and relationship between molecular structure and properties. Macromolecules 43, 2840 (2010).
24.Zhang, C., Guang, S.Y., Zhu, X.B., Xu, H.Y., Liu, X.Y., and Jiang, M.H.: Mechanism of dielectric constant variation of POSS-based organic-inorganic molecular hybrids. J. Phys. Chem. C 114, 22455 (2010).
25.Yang, B.H., Xu, H.Y., Yang, Z.Z., and Liu, X.Y.: Design and architecture of low-dielectric-constant organic-inorganic hybrids from octahydridosilsesquioxanes. J. Mater. Chem. 19, 9038 (2009).
26.Su, X.Y., Guang, S.Y., Xu, H.Y., Liu, X.Y., Li, S., Wang, X., Deng, Y., and Wang, P.: Controllable preparation and optical limiting properties of POSS-based functional hybrid nanocomposites with different molecular architectures. Macromolecules 42, 8969 (2009).
27.Zhu, Y.K., Guang, S.Y., and Xu, H.Y.: A versatile nanobuilding precursor for the effective architecture of well-defined organic/inorganic hybrid via click chemistry. Chin. Chem. Lett. 73, 1095 (2012).
28.Gujadhur, R., Venkataraman, D., and Kintigh, J.T.: Formation of aryl–nitrogen bonds using a soluble copper(I) catalyst. Tetrahedron Lett. 42, 4791 (2001).
29.Scaiano, J.C.: Handbook of Organic Photochemistry (CRC Press, Boca Raton, FL, 1989).
30.Pleux, L.L., Pellegrin, Y., Blart, E., Odobel, F., and Harriman, A.: Long-lived, charge-shift states in heterometallic, porphyrin-based dendrimers formed via click chemistry. J. Phys. Chem. A 115, 5069 (2011).
31.Luo, L. and Frisbie, C.D.: Length-dependent conductance of conjugated molecular wires synthesized by stepwise "click" chemistry. J. Am. Chem. Soc. 132, 8854 (2010).
32.Wild, A., Friebe, C., Winter, A., Hager, M.D., Grummt, U.W., and Schubert, U.S.: π-conjugated 2,2′:6′,2′′-bis(terpyridines): Systematical tuning of the optical properties by variation of the linkage between the terpyridines and the π-conjugated system. Eur. J. Org. Chem. 2010, 1859 (2010).
33.Saravanan, C., Senthil, S., and Kannan, P.: Click chemistry-assisted triazole-substituted azobenzene and fulgimide units in the pendant-based copoly(decylozymethacrylate)s for dual-mode optical switches. J. Polym. Sci., Part A: Polym. Chem. 46, 7843 (2008).
34.Lin, T.T., He, C., and Xiao, Y.: Theoretical studies of monosubstituted and higher phenyl-substituted octahydrosilsesquioxanes. J. Phys. Chem. B 107, 13788 (2003).
35.Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Montgomery, J.A.J., Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M., Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B., Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Nakatsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Klene, M., Li, X., Knox, J.E., Hratchian, H.P., 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., Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P., Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Daniels, A.D., Strain, M.C., Farkas, O., Malick, D.K., Rabuck, A.D., Raghavachari, K., Foresman, J.B., Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslowski, J., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Gonzalez, C., Pople, J.A., Gaussian 03, Revision A.1 (Gaussian, Inc. , Pittsburgh, PA, 2004).
36.Grisorio, R., Suranna, G.P., Mastrorilli, P., and Nobile, C.F.: Insight into the role of oxidation in the thermally induced green band in fluorene-based systems. Adv. Funct. Mater. 17, 538 (2007).
37.Yin, S.C., Xu, H.Y., Su, X.Y., Li, G., Song, Y.L., Lam, J., and Tang, B.Z.: Optical-limiting and nonlinear optical polyacetylenes: Synthesis of azobenzene-containing poly(1-alkyne)s with different spacer and tail lengths. J. Polym. Sci., Part A: Polym. Chem. 44, 2346 (2006).
38.Xue, L., Wan, L.Q., Hu, Y.H., Shen, X.N., Huang, F.H., and Du, L.: Thermal stability of a novel polytriazole resin. Thermochim. Acta 448, 147 (2006).
39.Sulaiman, S., Bhaskar, A., Zhang, J., Guda, R., Goodson, T., and Laine, R.M.: Molecules with perfect cubic symmetry as nanobuilding blocks for 3-D assemblies. Elaboration of octavinylsilsesquioxane. Unusual luminescence shifts may indicate extended conjugation involving the silsesquioxane core. Chem. Mater. 20, 5563 (2008).



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