Novel Highly Luminescent Amine-Functionalized Bridged Silsesquioxanes

Abstract : Amine-functionalized bridged silsesquioxanes (BSs) were synthesized from bis[(3-trimethoxysilyl)propyl] amine via a solvent-mediated route. BS-1 and BS-2 were obtained at neutral pH with sub-and stoichiometric amounts of water, respectively, and high tetrahydrofuran content. BS-3 was prepared with hyperstoichiometric water concentration, high tetrahydrofuran content, and hydrochloric acid. BS-4 was synthesized with hyperstoichiometric water concentration, high ethanol content, and sodium hydroxide. BS-1 and BS-2 were produced as transparent films, whereas BS-3 and BS-4 formed white powders. Face-to-face stacking of flat or folded lamellae yielded quasi-hydrophobic platelets with emission quantum yields of 0.05 ± 0.01 (BS-1 and BS-2) or superhydrophilic onion-like nanoparticles with exciting emission quantum yields of 0.38 ± 0.03 (BS-3) and 0.33 ± 0.04 (BS-4), respectively. The latter two values are the largest ever reported for amine-functionalized siloxane-based hybrids lacking aromatic groups. Fast Grotthus proton hopping between =NH + 2 /=NH groups (BS-3) and =N − /=NH groups (BS-4), promoted by H + and OH − ions, respectively, and aided by short amine-amine contacts provided by the onion-like morphology, account for this unique optical behavior.
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Dernière modification le : jeudi 9 mai 2019 - 11:28:16

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Rui Pereira, Silvia Nunes, Guillaume Toquer, Marita Cardoso, Artur Valente, et al.. Novel Highly Luminescent Amine-Functionalized Bridged Silsesquioxanes. Frontiers in Chemistry, Frontiers, 2018, 5, ⟨10.3389/fchem.2017.00131⟩. ⟨hal-02105855⟩

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