7. Experimental Section
7.5 Nanoparticle Syntheses and Functionalization
7.5.7 Determination of PbS Quantum Dot Concentration
The concentration of the PbS nanocrystals synthesized according to Moreels et al. was estimated as following: A conversion of 70% of the limiting precursor was assumed. From the particle diameter derived from TEM images, the volume of a single particle was calculated (assuming spherical particles). With the density of PbS and the amount of PbS that can be formed, the number of particles and their concentration was estimated to be 5 × 10-5 mol/L.
7.5 Nanoparticle Syntheses and Functionalization
7.5.8 Functionalization of PbS Quantum Dots for Surface Initiated Suzuki-Miyaura Coupling Polymerization
PbS quantum dots (2.5 mL) were precipitated by the addition of 5.5 mL of ethanol. After centrifugation and removal of the supernatant, the precipitate was redispersed in 4 mL of toluene.
After a second precipitation by addition of ethanol and a subsequent centrifugation step, the particles were dispersed in 1 mL of THF. 10 mg (0.03 mmol) of the respective carboxylate ligand were added and the mixture was stirred at 50 °C overnight.
7.5.9 Synthesis of Surface-Immobilized Initiator Complexes
1 mL of a QD dispersion functionalized with the respective halo-aryl ligand in toluene or in THF was degassed by applying three freeze-pump-thaw cycles. Afterwards, [Pd(PtBu3)2] or [Pd(dba)2] with 1.5 equiv. of PtBu3,were added and the mixture was stirred at room temperature or heated to the desired temperature.
7.5.10 Surface Initiated Suzuki-Miyaura Coupling Polymerization Procedure
In a 100 mL Schlenk tube, 100 mg (0.17 mmol, 1 equiv.) of monomer, 102 mg (0.17 mmol, 4 equiv.) of CsF and 355 mg (1.346 mmol, 8 equiv.) of 18 crown 6 were dissolved in 25 mL of THF and 1 mL of water. After degassing the solution by 3 freeze-pump-thaw cycles, the QD/initiator dispersion was quickly injected. After 1 hour at a temperature between -20 °C and room temperature, the polymerization was quenched by the addition of 15-25 mL of methanol. The hybrid particles were collected by centrifugation (typically at 2400 g for 7 min) and were redispersed in 10 mL of toluene. For end-capping experiments, the polymerization was quenched after 1 hour polymerization time by the addition of 20 equiv. of 2-[3,5-bis(trifluoromethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (vs. 1 equiv. of [Pd(PtBu3)2]), stirred for another 30 minutes at 0 °C, followed by the addition of methanol to precipitate the hybrid particles.
7.5.11 Polymer Isolation after Surface Initiated Suzuki-Miyaura Coupling Polymerization
reduced pressure. The resulting polymer was dissolved in 2 mL of hot toluene and filtered through a syringe filter directly into 4 mL of MeOH to precipitate the polymer. After centrifugation, the supernatant solution was discarded and the isolated polymer dried under reduced pressure.
7.6 Nanoparticle-Ligand Syntheses
7.6.1 Synthesis of Benzo[c][2,1,3]thiadiazole218
In a round bottom flask, 8.3 g (76.9 mmol) of 1,2-diaminobenzene were dissolved in 140 mL of dichloromethane and 33.2 mL of triethyl amine. Through a dropping funnel, 10 g (84.4 mmol) of SOCl2 were added over a time period of 2 hours. After heating overnight to 60 °C, the solvent was removed under reduced pressure and the residue was isolated by steam distillation. The product was obtained as colorless crystals in nearly quantitative yield.
1H-NMR (400 MHz, CDCl3, 25 °C) δ = 8.02 (m, 2H), 7.59 (m, 2H) ppm.
7.6.2 Synthesis of 4-Bromobenzo[c][2,1,3]thiadiazole219
In a 3-neck round bottom flask, 3.012 g (22.2 mmol) of benzo[c][2,1,3]thiadiazole were dispersed in 22.2 mL of HBr (47 wt% aq.) and heated to 100 °C. 1.04 mL (22.2 mmol) of bromine were slowly added through a dropping funnel and the mixture was refluxed overnight. After addition of 30 mL of water, the mixture was neutralized with K2CO3 and the aqueous phase was extracted with chloroform. After removal of the solvent, the product was purified by column chromatography (dichloromethane) and crystallized from ethanol resulting in 34% yield.
1H-NMR (400 MHz, CDCl3, 25 °C)
δ = 7.98 (dd, 3JHH = 8.8, 4JHH = 0.9 Hz, 1H), 7.85 (dd, 3JHH = 7.2, 4JHH = 0.9 Hz, 1H), 7.48 (dd, 3JHH = 8.8, 3JHH = 7.2 Hz, 1H) ppm.
7.6 Nanoparticle-Ligand Syntheses
7.6.3 Synthesis of Methyl benzo[c][2,1,3]thiadiazole-4-carboxylate220
In a 50 mL Schlenk tube under inert gas atmosphere, 173 mg (0.232 mmol) of [Pd(dppf)Cl2] were dissolved in 8 mL of methanol and 0.64 mL of NEt3. A 22 mL stainless steel pressure reactor with glass inlet was charged with 509.5 mg (2.36 mmol) of 4-bromobenzo[c][2,1,3]thiadiazole and was set under inert gas atmosphere. After addition of the content of the Schlenk tube, the reactor was pressurized with CO (20 bar). The mixture was stirred at 120 °C for 16 h. The resulting red-brown solid was dissolved in methanol and filtrated over silica. The solvent was removed under reduced pressure and the product was crystallized from ethanol (crystallization at -30 °C), yielding 330 mg (73%) of the desired product as red-brown crystals.
1H-NMR (400 MHz, CD3OD, 25 °C)
δ = 8.41 (dd, 4JHH = 7.0, 5JHH = 1.1 Hz, 1H, H1), 8.31 (dd, 3JHH = 8.8, 4JHH = 1.1 Hz, 1H, H3), 7.81 (dd, 3JHH = 8.8, 3JHH = 7.0 Hz, 1H, H2), 4.05 (s, 3H, H4) ppm.
7.6.4 Synthesis of Methyl 7-bromobenzo[c][2,1,3]thiadiazole-4-carboxylate
In an 8 mL vial, 220 mg (1.13 mmol) of methyl benzo[c][2,1,3]thiadiazole-4-carboxylate were dissolved in 0.5 mL of H2SO4 (97% aq.). The mixture was heated to 60 °C and 120 mg (0.67 mmol) of N-bromosuccinimide were added. After 1 h, another 120 mg (0.67 mmol) of N-bromosuccinimide
7.6.5 Synthesis of 7-Bromobenzo[c][2,1,3]thiadiazole-4-carboxylic acid
In a 25 mL Schlenk tube, 204 mg (0.74 mmol) of methyl 7-bromobenzo[c][2,1,3]thiadiazole-4-carboxylate were dissolved in 9 mL of THF and 1 mL of water. After the addition of 100 mg of KOH, the mixture was stirred at 50 °C for 2 hours. After neutralizing with 2 M aqueous HCl solution, the desired product was extracted from the aqueous solution with chloroform. The solvent of the combined organic phases was removed under reduced pressure, yielding 120 mg (62%) of the desired product as red-brown crystals.
1H-NMR (400 MHz, CD3OD, 25 °C)
δ = 8.24 (d, 3JHH = 7.6 Hz, 1H, H2), 8.02 (d, 3JHH = 7.6 Hz, 1H, H3) ppm.
13C-NMR (101 MHz, CD3OD, 25 °C)
δ = 166.9 (C7), 155.3 (C6), 152.9 (C5), 135.1 (C3), 132.8 (C2), 124.1 (C4), 120.8 (C1) ppm.
7.7 Embedding Experiments
7.7.1 Encapsulation of Quantum Dots and Organic/Inorganic Semiconductor Hybrid Particles into Polymer Nanoparticles by Miniemulsion Polymerization
A 100 mL Schlenk tube was charged with 20 to 200 mg of sodium dodecyl sulfate and 80 mL of degassed water. In an 8 mL vial, 5 to 20 mg of azobisisobutyronitrile, the respective volume of a quantum dot or hybrid particle dispersion in toluene, 0.1 mL to 1 mL of monomer, 0.1 mL of hexadecane and 0.01 to 0.5 mL of ethylene glycol dimethacrylate were mixed. The mixture was added to the aqueous sodium dodecyl sulfate solution under vigorous stirring and a miniemulsion was generated by ultrasonication (Bandelin GM3200 ultrasonotrode with KE76 tip, operated at 120 W) with an intensity of 60% for 2 to 3 minutes while the Schlenk tube was placed in an ice bath. For polymerization, the miniemulsion was stirred at 76 °C for 5 hours under a nitrogen atmosphere followed by stirring overnight at room temperature in an open vessel.
7.8 Force Spectroscopy on Poly(Methyl Methacrylate) Particles with Atomic Force Microscopy
7.7.2 Synthesis of Polymer Nanoparticles and Embedding of Quantum Dots by Multi-Inlet Vortex Mixing
A THF/polymer solution was generated by dissolving the respective polymer in THF under ultrasonication followed by stirring the solution for 30 minutes at 50 °C. In the case of QD-embedding experiments, the QDs were precipitated from toluene by the addition of methanol and redispersed in the THF/polymer mixture by ultrasonication. The polymer solution or polymer/QD dispersion was filtrated through a syringe filter before being used in vortex experiments.
7.7.3 Encapsulation of Quantum Dots and Organic/Inorganic Semiconductor Hybrid Particles into Silica Nanoparticles
For the embedding into silica, the respective quantum dots or hybrid particles were precipitated from toluene with ethanol. After centrifugation, the supernatant was removed and the particles were redispersed in 1 mL of cyclohexane. In an 8 mL vial, 225 mg of Igepal CO-520 were dissolved in 4.4 mL of cyclohexane, added to the quantum dot dispersion, followed by stirring the mixture for 30 minutes. 60 µL of NH3 in water (25 wt%) were added and the inhomogeneous mixture was stirred for another 60 minutes. After addition of 20 to 400 µL of tetraethyl orthosilicate the reaction mixture was vigorously stirred for 24 hours at room temperature. The resulting particles were isolated by precipitation with 2 mL of ethanol followed by centrifugation. After removal of the supernatant, the particles were redispersed in 4 mL of water.
7.8 Force Spectroscopy on Poly(Methyl Methacrylate) Particles with Atomic Force Microscopy
For the recording of force-distance curves, the polymer dispersions were diluted by a factor of 200 and spin coated onto a plasma cleaned silica substrate. For analysis of the data, the JPK data processing software was used. The spring constant of the Bruker OTESPA-R3 cantilever was 26 N/m while the sensitivity was set to 25 nm/V. Before applying the Hertz model, first the baseline
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9. Appendix
Figure A 1. Typical 1H-NMR spectrum of BOC-aniline functionalized polyfluorene recorded at room temperature in C6D6.
Figure A 3. GPC trace of BOC-aniline functionalized polyfluorene after deprotection at 190 °C under reduced pressure.
A bimodal distribution is observed due to the reaction of aniline functionalized polymer with isocyanate functionalized polymer, resulting in urea coupled species.
Figure A 4. GPC trace of aniline functionalized polyfluorene after deprotection with trifluoroacetic acid.
Appendix
Figure A 5. Typical 1H-NMR spectrum of phenylphosphonic acid diethyl ester functionalized polyfluorene recorded at room temperature in C6D6.
Figure A 6. Typical GPC trace of phenylphosphonic acid diethyl ester functionalized polyfluorene.
Figure A 7. Typical GPC trace of phenylphosphonic acid functionalized polyfluorene.
Figure A 8. MALDI-TOF mass spectra of polyfluorene obtained after initiating the polymerization with [(bromo)(phenyl)(tri-tert-butylphosphine)Pd(II)] and quenching after 30 minutes with conc. HCl (top), with
1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)diphenyl disulfide (center) and with 4-mercaptophenylboronic acid (bottom).
Appendix
Figure A 9. GPC traces of polymers isolated from polymerizations of 2-(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane initiated by [(bromo)(phenyl)(tri-tert-butylphosphine)Pd(II)] and quenched by the addition of concentrated HCl (left), 4-mercaptophenylboronic acid (center) and by the addition of
1,2-bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)diphenyl disulfide (right).
Figure A 10. GPC trace of polymer obtained from a polymerization of 2-(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane initiated by [(bromo)(phenyl)(tri-tert-butylphosphine)Pd(II)] and quenched by the
addition of 4,4,5,5-tetramethyl-2-(4-(tritylthio)phenyl)-1,3,2-dioxaborolane.
Figure A 11. MALDI-TOF mass spectrum of polyfluorene obtained after initiating the polymerization with [(bromo)(phenyl)(tri-tert-butylphosphine)Pd(II)] and quenching the polymerization by the addition of sulfur dissolved in
THF. In the inset, the MALDI-TOF mass signal of the thiol-functionalized 6-mer is depicted, together with the calculated isotope pattern of this species (red line).
Figure A 12. GPC traces of polymers obtained from polymerizations of 2-(7-bromo-9,9-dioctyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (right) and of 2-(5-bromo-4-(2-ethylhexyl)thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (left) initiated with [(bromo)(phenyl)(tri-tert-butylphosphine)Pd(II)] and quenched by the addition
of sulfur, respectively.