1. Novel Highly Luminescent Amine-Functionalized Bridged Silsesquioxanes
- Author
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Luís D. Carlos, M. A. Cardoso, Guillaume Toquer, Verónica de Zea Bermudez, Rute A. S. Ferreira, Marta C. Ferro, Artur J.M. Valente, S. C. Nunes, Maria Manuela Silva, Rui F. P. Pereira, Departamento de Matemática e Aplicaçoes (DMA), Universidade do Minho, Universidade da Beira Interior, Nanomatériaux pour l'Energie et le Recyclage (LNER), Institut de Chimie Séparative de Marcoule (ICSM - UMR 5257), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Instituto Português de Oncologia de Lisboa, Francisco Gentil, Departemento de Fisica and CICECO, Universidade de Aveiro, Department of Chemistry and CQ-VR, University of Trás-os-Montes e Alto Douro, Universidade do Minho = University of Minho [Braga], University of Beira Interior [Portugal] (UBI), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)
- Subjects
Nanoparticle ,Hydrochloric acid ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,lcsh:Chemistry ,chemistry.chemical_compound ,Polymer chemistry ,morphology ,luminescence ,Tetrahydrofuran ,Original Research ,Science & Technology ,General Chemistry ,[CHIM.MATE]Chemical Sciences/Material chemistry ,sol-gel chemistry ,021001 nanoscience & nanotechnology ,solvent-assisted structuring ,0104 chemical sciences ,Chemistry ,lcsh:QD1-999 ,chemistry ,Sodium hydroxide ,Siloxane ,bis[(3-trimethoxysilyl)propyl]amine ,bis[(3-trimethoxysilyl) propyl] amine ,Amine gas treating ,0210 nano-technology ,Luminescence ,Stoichiometry - 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 = [Formula: see text]/ = 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., This work was supported by Fundacao para a Ciencia e a Tecnologia (FCT)/MEC and FEDER (contracts UID/QUI/00616/2013, POCI-01-0145-FEDER-007491, and UID/Multi/00709/2013) and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement, project UniRCell (Ref. SAICTPAC/0032/2015, POCI-01-0145-FEDER-016422), and project LUMECD (Ref. PTDC/CTM/NAN/0956/20149 and POCI-01-0145-FEDER-016884). RP and MC acknowledge FCT for grants SFRH/BPD/87759/2012 and SFRH/BD/118466/2016, respectively. SN also acknowledges FCT for grants SFRH/BPD/63152/2009 and Post-PhD Fellowship of LUMECD project. This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, POCI-01-0145-FEDER-007679 (FCT-Ref. UID/CTM/50011/2013), financed by national funds through the FCT/MEC and when appropriate co-financed by FEDER under the PT2020 Partnership Agreement.
- Published
- 2018
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