Design and synthesis of multi-functional silsesquioxane nanoparticles having two distinct optoelectronic functionalities
- 139 Downloads
Multi-functional silsesquioxane nanoparticles (SQ-NPs) having two distinct optoelectronic functionalities on a single arm were prepared using a thiol-epoxy click reaction followed by esterification. The epoxy-functionalized SQ-NPs were prepared from commercially available (3-glycidyloxypropyl)triethoxysilane and were employed in the thiol-epoxy click reaction to introduce aromatic and heterocyclic thiol compounds, such as naphthalenethiol, 2-mercapto-1-methylimidazole, and 4,5-diphenyl-2-oxazolethiol. The resulting hydroxyl-functionalized SQ-NPs were further functionalized via esterification to incorporate a second functional group. The X-ray diffraction (XRD), size-exclusion chromatography (SEC), and scanning force microscopy (SFM) results indicated the formation of SQ-NPs (< 5 nm) with relatively narrow size distributions and no aggregation. Multi-functional SQ-NPs containing peripheral electron-accepting benzothiazole moieties were also synthesized using 2-mercaptobenzothiazole. The resulting SQ-NPs showed good solubility, high refractive indices (1.55–1.62), high thermal stability (Td5 > 300 °C), and characteristic optoelectronic properties with a wide range of Stokes shifts (5200–12,000 cm−1). The optoelectronic properties of the multi-functional SQ-NPs could be controlled by modifying the structure of the two distinct functional groups, which could be easily tuned by varying the structure of the thiol compounds and acid chloride derivatives in the feed.
KeywordsSilsesquioxane Multi-functional nanoparticles Optoelectronic functionalities Organic-inorganic hybrid
There was no financial support obtained for the reported work.
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 1.Cordes DB, Lickiss PD, Rataboul F (2010) Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chem Rev 110:2081–2173Google Scholar
- 2.Gunawidjaja R, Huang F, Gumenna M, Klimenko N, Nunnery GA, Shevchenko V, Tannenbaum R, Tsukruk VV (2009) Bulk and surface assembly of branched amphiphilic polyhedral oligomer silsesquioxane compounds. Langmuir 25:1196–1209Google Scholar
- 24.Lin H, Chen L, Ou J, Liu Z, Wang H, Dong J, Zou H (2015) Preparation of well-controlled three-dimensional skeletal hybrid monoliths via thiol-epoxy click polymerization for highly efficient separation of small molecules in capillary liquid chromatography. J Chromatogr A 1416:74–82CrossRefGoogle Scholar
- 37.Laine RM, Roll MF (2011) Polyhedral phenylsilsesquioxanes. Macromolecules 44:1073–1109Google Scholar
- 42.Choi J-K, Lee D-H, Rhee S-K, Jeong H-D (2010) Observation of tunable refractive indices and strong intermolecular interactions in newly synthesized methylene-biphenylene-bridged silsesquioxane thin films. J Phys Chem C 144:14233–14239Google Scholar
- 44.Chen Y-H, Lin L-Y, Lu C-W, Lin F, Huang Z-Y, Lin H-W, Wang PH, Liu YH, Wong KT, Wen J, Miller DJ, Darling SB (2012) Vacuum-deposited small-molecule organic solar cells with high power conversion efficiencies by judicious molecular design and device optimization. J Am Chem Soc 134:13616–13623CrossRefGoogle Scholar
- 46.Alfonso M, Espinosa A, Tárraga A, Molina P (2014) Multifunctional benzothiadiazole-based small molecules displaying solvatochromism and sensing properties toward nitroarenes, anions, and cations. Chem Open 3:242–249Google Scholar
- 47.Neto BAD, Lapis AAM, da Silva Júnior EN, Dupont J (2013) 2,1,3-Benzothiadiazole and derivatives: synthesis, properties, reactions, and applications in light technology of small molecules. Eur J Org Chem 2013:228–255Google Scholar
- 50.Liu X, Hsu BBY, Sun Y, Mai C-K, Heeger AJ, Bazan GC (2014) High thermal stability solution-processable narrow-band gap molecular semiconductors. J Am Chem Soc 136:16144–16147Google Scholar
- 52.Fu B, Baltazar J, Hu Z, Chien A-T, Kumar S, Henderson CL, Collard DM, Reichmanis E (2012) High charge carrier mobility, low band gap donor−acceptor benzothiadiazole-oligothiophene based polymeric semiconductors. Chem Mater 24:4123–4133Google Scholar