The synthesis of a novel polyhedral oligomeric silsesquioxane functionalized with eight rigid and directional terpyridine-based arms (Ter-POSS) was successfully achieved via a Sonogashira reaction. The POSS based ligand was extensively characterized using different techniques including 1H, 13C and 29Si NMR as well as UV-Vis and fluorescence spectroscopies. The assembly of these nano-caged units in the presence of different transition metal ions (Fe2+, Zn2+ and Cu2+) as well as of a cation from the lanthanides (Eu3+) was investigated using absorption and emission spectroscopies. The final materials display an evident emission in different regions of the visible spectrum as a function of the cation employed. Additional insights into the structural organization of Ter-POSS in the presence of metal cations were obtained via molecular mechanics and molecular dynamics simulations. The polymeric material resulting from the complexation with europium displays a white light emission ascribed to the presence of combined contributions from the blue, green and red regions. The final self-assembled organizations display an increased quantum yield with the highest value (29.6%) obtained in the presence of Zn2+. Moreover, the white-light emitting europium-based nanostructure exhibits one of the highest quantum yields reported in the literature for similar solids.

Santiago-Portillo A., Cina Valerio, Carbonell E., Fusaro L., Lemaur V., Lazzaroni R., et al. (2022). White light emitting silsesquioxane based materials: The importance of a ligand with rigid and directional arms. MATERIALS ADVANCES, 3(1), 570-578 [10.1039/d1ma00801c].

White light emitting silsesquioxane based materials: The importance of a ligand with rigid and directional arms

Cina Valerio;Fusaro L.;Gruttadauria M.;Giacalone F.
;
Aprile C.
2022

Abstract

The synthesis of a novel polyhedral oligomeric silsesquioxane functionalized with eight rigid and directional terpyridine-based arms (Ter-POSS) was successfully achieved via a Sonogashira reaction. The POSS based ligand was extensively characterized using different techniques including 1H, 13C and 29Si NMR as well as UV-Vis and fluorescence spectroscopies. The assembly of these nano-caged units in the presence of different transition metal ions (Fe2+, Zn2+ and Cu2+) as well as of a cation from the lanthanides (Eu3+) was investigated using absorption and emission spectroscopies. The final materials display an evident emission in different regions of the visible spectrum as a function of the cation employed. Additional insights into the structural organization of Ter-POSS in the presence of metal cations were obtained via molecular mechanics and molecular dynamics simulations. The polymeric material resulting from the complexation with europium displays a white light emission ascribed to the presence of combined contributions from the blue, green and red regions. The final self-assembled organizations display an increased quantum yield with the highest value (29.6%) obtained in the presence of Zn2+. Moreover, the white-light emitting europium-based nanostructure exhibits one of the highest quantum yields reported in the literature for similar solids.
Settore CHIM/06 - Chimica Organica
Santiago-Portillo A., Cina Valerio, Carbonell E., Fusaro L., Lemaur V., Lazzaroni R., et al. (2022). White light emitting silsesquioxane based materials: The importance of a ligand with rigid and directional arms. MATERIALS ADVANCES, 3(1), 570-578 [10.1039/d1ma00801c].
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/10447/532751
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