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A Direct Approach to Organic/Inorganic Semiconductor Hybrid Particles via Functionalized Polyfluorene Ligands
Authors:Tjaard de Roo  Johannes Haase  Janine Keller  Christopher Hinz  Marius Schmid  Denis V Seletskiy  Helmut Cölfen  Alfred Leitenstorfer  Stefan Mecking
Affiliation:1. Chair of Chemical Materials Science, University of Konstanz, Germany;2. Department of Physics and Center for Applied Photonics, University of Konstanz, Germany;3. Chair of Physical Chemistry, Department of Chemistry, University of Konstanz, Germany
Abstract:Controlled Suzuki–Miyaura coupling polymerization of 7′‐bromo‐9′,9′‐dioctyl‐fluoren‐2′‐yl‐4,4,5,5‐tetramethyl‐1,3,2]dioxaborolane initiated by bromo(4‐tert‐butoxycarbonylamino‐phenyl)(tri‐tert‐butylphosphine)palladium ( 1 ) or bromo(4‐diethoxyphosphoryl‐phenyl)(tri‐tert‐butylphosphine)palladium ( 2 ) yields functionalized polyfluorenes (Mn = 4 × 103 g mol?1, Mw/Mn < 1.2) with a single amine or phosphonic acid, respectively, end‐group. High temperature synthesis of cadmium selenide quantum dots with these functionalized polyfluorenes as stabilizing ligands yields hybrid particles consisting of good quality (e.g. emission full width at half maximum of 30 nm; size distribution σ < 10%) inorganic nanocrystals with polyfluorene attached to the surface, as corroborated by transmission electron microscopy analysis and analytical ultracentrifugation. Sedimentation studies on particle dispersions show that a substantial portion (ca. half) of the phosphonic acid terminated polyfluorene ligands is bound to the inorganic nanocrystals, versus ca. 5% for the amino‐functionalized polyfluorene ligands. Single particle micro‐photoluminescence spectroscopy shows an efficient and complete energy transfer from the polyfluorene layer to the inorganic quantum dot.
Keywords:end‐group‐functionalization  Suzuki–  Miyaura coupling  polymerization  hybrid particles  analytical ultracentrifugation  energy transfer
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