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Luminescent Blooming of Dendronic Carbon Nanotubes through Ion‐Pairing Interactions with an EuIII Complex
Authors:Laura Maggini  Dr. Francesca Maria Toma  Dr. Luigi Feruglio  Joanna M. Malicka  Dr. Tatiana Da Ros  Dr. Nicola Armaroli  Prof. Maurizio Prato  Dr. Davide Bonifazi
Affiliation:1. Department of Chemistry, University of Namur (FUNDP), Rue de Bruxelles 61, 5000 Namur (Belgium);2. Department of Chemical and Pharmaceutical Sciences and UdR INSTM, University of Trieste, Piazzale Europa 1, 34127 Trieste (Italy);3. Molecular Photoscience Group, Istituto per la Sintesi Organica e la Fotoreattività del CNR (ISOF‐CNR), Via P. Gobetti 101, 40129 Bologna (Italy)
Abstract:A multiwalled carbon nanotube (MWCNT) scaffold was covalently functionalized with a second‐generation polyamidoamine (PAMAM) dendron, presenting four terminal amino groups per grafted aryl moiety. These reactive functions were alkylated to obtain a positively charged polycationic dendron/carbon nanotube system ( d‐MWCNTs?Cl ), which eventually underwent anion exchange reaction with a negatively charged and highly luminescent EuIII complex ( [EuL4]?NEt4 , in which L =(2‐naphtoyltrifluoroacetonate)). This process afforded the target material d‐MWCNTs?[EuL4] , in which MWCNTs are combined with red‐emitting EuIII centers through electrostatic interactions with the dendronic branches. Characterization of the novel MWCNT materials was accomplished by means of TGA and TEM, whereas d‐MWCNTs?Cl and d‐MWCNTs? [EuL4] further underwent XPS, SEM and Raman analyses. These studies demonstrate the integrity of the luminescent [EuL4]? center in the luminescent hybrid, the massive load of the cationic binding sites, and the virtually complete anion‐exchange into the final hybrid material. The occurrence of the ion‐pairing interaction with MWCNTs was unambiguously demonstrated through DOSY NMR diffusion studies. Photophysical investigations show that MWCNTs?[EuL4] is a highly soluble and brightly luminescent red hybrid material in which MWCNTs act as photochemically inert scaffolds with negligible UV/Vis absorption, compared with the grafted Eu complex, and with no quenching activity. The high dispersibility of MWCNTs?[EuL4] in a polymer matrix makes it a promising luminophore for applications in material science.
Keywords:dendrimers  ion‐pairing  lanthanides  luminescence  nanotubes  NMR spectroscopy
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