Synthesis of Initiator Precursors and Complexes

Gel permeation chromatography: Gel permeation chromatography was carried out on a Polymer Laboratories PL-GPC 50 with two PLgel 5 µm MIXED-C columns in THF at 50 °C with RI detection against polystyrene standards.

Nuclear magnetic resonance spectroscopy: NMR spectra were recorded on a Varian Unity INOVA 400 and on a Bruker Avance 400 spectrometer (¹H: 400 MHz, ¹³C: 101 MHz, ¹⁹F: 376 MHz,

31P: 162 MHz). ¹H-NMR and ¹³C-NMR chemical shifts were referenced to the residual signal of the deuterated solvent. Multiplicities are given as follows: s: singlet, d: doublet, t: triplet, q: quartet, m:

multiplet.

Matrix-assisted LASER desorption/ionization – time of flight spectrometry: For MALDI-TOF MS, the polymer was dissolved in CHCl3 and analyzed by a Bruker Microflex MALDI-TOF with alpha-cyano-4-hydroxycinnamic acid as a matrix.

Dynamic light scattering: Particle size measurements were performed on a Malvern Nano-ZS ZEN 3600 particle sizer (173° back scattering, 633 nm LASER wavelength). The Malvern dispersion technology software 5.1 algorithm was used to analyze the autocorrelation function, yielding number weighted particle sizes and size distributions. Fluorescent polyfluorene particles obtained by multi-inlet vortex mixing experiments were analyzed by a Viscotek 802DLS (830 nm LASER wavelength), to prevent excitation of the sample during particle size analysis.

Atomic force microscopy: AFM manipulation was carried out with a JPK Nanowizard 3 NanoScience AFM instrument. For force-spectroscopy, OTESPA-R3 cantilevers from Bruker were used.

Centrifugation: A Biofuge Primo centrifuge with a highconic rotor (6 × 50 mL) was used (diameter: 12.4 cm).

Differential scanning calorimetry: DSC analysis was performed on a Netzsch DSC 204 F1 at a heating rate of 10 °C/min in a temperature range from -50 °C to 150 °C.

7.2 Synthesis of Initiator Precursors and Complexes

7.2.1 Synthesis of [Bis(tri-tert-butylphosphine)palladium(0)]²⁰³

δ = 1.52 (t, ³JPH = 5.6 Hz, 54H) ppm.

31P{¹H}-NMR (162 MHz, C6D6, 25 °C) δ = 98.3 ppm.

7.2.2 Synthesis of Diethyl-(4-bromophenyl)phosphonate²¹⁰

To a solution of 8.0 g (28.3 mmol) of 1-bromo-4-iodobenzene and 572.5 mg (0.5 mmol) of [Pd(PPh3)4] in 100 mL of toluene, 3.0 g (29.4 mmol) of NEt3 and 3.9 g (28.3 mmol) of diethyl phosphonate were added. The mixture was heated to 55 °C for 84 h. The conversion was monitored by ³¹P-NMR. After complete conversion of diethyl phosphonate, salts formed were filtered off and the solvent was removed from the filtrate. The desired product was purified by column chromatography (pentane:ethyl acetate, 1:1) and obtained in 70% yield.

1H-NMR (400 MHz, CDCl3, 25 °C)

δ = 7.63 (m, 4H, H1/2), 4.10 (m, 4H, H3), 1.31 (t, ³JPH = 7.1 Hz, 6H, H4) ppm.

31P{¹H}-NMR (162 MHz, CDCl3, 25 °C) δ = 17.7 ppm.

7.2.3 Synthesis of [(Bromo)(4-diethoxyphosphoryl-phenyl)(tri-tert -butylphosphine)palladium]⁶⁴

A 25 mL Schlenk tube was charged with 100 mg (0.2 mmol) of [Pd(P^tBu3)2], 90 mg (0.3 mmol) of diethyl-(4-bromophenyl)phosphonate and 10 mL of 2-butanone. The reaction mixture was stirred at 75 °C for 3 hours. After addition of pentane, the dispersion was treated in an ultrasonic bath and the yellow precipitate was collected by centrifugation. The latter was washed with pentane and treated by ultrasound several times to yield the desired complex in 21% yield as a yellow powder.

7.2 Synthesis of Initiator Precursors and Complexes

1H-NMR (400 MHz, C6D6, 25 °C)

δ = 7.57 (m, 4H, H1/2), 3.94 (m, 4H, H3), 1.02 (t, ³JHH = 7.0 Hz, 6H, H4), 0.94 (d, ³JPH = 12.6 Hz, 27H, H of P^tBu3) ppm.

31P{¹H}-NMR (162 MHz, C6D6, 25 °C) δ = 61.8 (P^tBu3), 19.1 (phosphonate) ppm.

7.2.4 Synthesis of [(Bromo)(4-tert-butoxycarbonylamino-phenyl)(tri-tert -butylphosphine)palladium]⁶⁴

In a 25 mL Schlenk tube, 200 mg (0.39 mmol) of [Pd(P^tBu3)2] and 318 mg (1.17 mmol) of N-(tert-butoxycarbonyl)-4-bromoaniline were dissolved in 12 mL of 2-butanone. After stirring the mixture at 75 °C for one hour, the solvent was removed under reduced pressure. The yellow residue was mixed with pentane and placed in an ultrasonic bath for 30 minutes. The resulting yellow powder was collected by centrifugation and washed with pentane several times, to yield the desired product in 39% yield as yellow powder.

1H-NMR (400 MHz, C6D6, 25 °C)

δ = 7.29 (dd, ³JHH = 9.0 Hz, ⁴JPH = 2.2 Hz, 2H, H1), 7.05 (d, ³JHH = 9.0 Hz, 2H, H2), 5.99 (s, 1H, H3), 1.43 (s, 9H, H4), 1.01 (d, ³JPH = 12.4 Hz, 27H, H of P^tBu3) ppm.

31P{¹H}-NMR (162 MHz, C6D6, 25 °C) δ = 62.6 ppm.

7.2.5 Synthesis of [(Bromo)(phenyl)(tri-tert-butylphosphine)palladium]⁴⁹

precipitate was collected by centrifugation and was washed with pentane three times to yield the desired complex in 72% yield as yellow powder.

1H-NMR (400 MHz, C6D6, 25 °C)

δ = 7.42 (m, 2H, H1), 6.82 (m, 2H, H2), 6.76 (m, 1H, H3), 1.01 (d, ³JPH = 12.5 Hz, 27H, H of P^tBu3) ppm.

31P{¹H}-NMR (162 MHz, C6D6, 25 °C) δ = 62.5 ppm.

7.2.6 Synthesis of 1-Bromo-4-[[(1,1-dimethylethyl)dimethylsilyl]thio]benzene²¹¹

In a Schlenk tube, 1.0 g (5.3 mmol) of 4-bromothiophenol were dissolved in 25 mL of THF and cooled to 0 °C. In a second Schlenk tube, 0.14 g (5.82 mmol) of NaH were dispersed in 25 mL of THF and cooled to 0 °C. The 4-bromothiophenol solution was added dropwise to the NaH dispersion in THF and the resulting mixture was stirred for 3 h until gas evolution ceased. In a third Schlenk tube, 1.20 g (7.9 mmol) of tert-butyl(chloro)dimethyl silane were dissolved in 5 mL of THF and were added dropwise at 0 °C to the deprotonated thiol. After stirring for 1 h at 0 °C and 70 h at room temperature, the reaction mixture was filtrated over diatomaceous earth. After removal of the solvent, the desired product was isolated by distillation (142 °C, 5 mbar) and obtained as colorless solid in 70% yield.

1H-NMR (400 MHz, CDCl3, 25 °C)

δ = 7.36 (m, 2H, H1), 7.29 (m, 2H, H2), 0.97 (s, 9H, H3), 0.18 (s, 6H, H4) ppm.

13C-NMR (101 MHz, CDCl3, 25 °C)

δ = 137.2 (C6), 131.9 (C1), 131.0 (C2), 121.3 (C7), 26.6 (C3), 19.1 (C5), -3.1 (C4) ppm.

7.2.7 Synthesis of Carbamothioic acid, N-phenyl-, S-(4-bromophenyl) ester²¹²

7.2 Synthesis of Initiator Precursors and Complexes

In a round bottom flask, 1.88 g (10 mmol) of 4-bromothiophenol and 1.19 g (10 mmol) of phenyl isocyanate were heated to 75 °C and stirred for 1 h. After addition of 20 mL of CH2Cl2, the solution was stirred for 14 h at room temperature. Crystallization from Et2O yielded the desired product in quantitative yield as colorless crystals.

1H-NMR (400 MHz, acetone-d6, 25 °C)

δ = 9.49 (s, 1H, H3), 7.62 (d, ³JHH = 7.9 Hz, 2H, H1), 7.57 (d, ³JHH = 8.2 Hz, 2H, H4), 7.50 (d,

3JHH = 7.9 Hz, 2H, H2), 7.32 (m, 2H, H5), 7.09 (t, ³JHH = 7.4 Hz, 1H, H6) ppm.

13C-NMR (101 MHz, acetone-d6, 25 °C)

δ = 163.2 (C9), 139.8 (C10), 137.9 (C2), 132.9 (C1), 129.8 (C5), 129.0 (C8), 124.8 (C6), 124.0 (C7), 120.2 (C4) ppm.

7.2.8 Synthesis of 1-Bromo-4-triphenylmethylsulfanylbenzene²¹³

In a round bottom flask, 4 g (15 mmol) of triphenylmethanol were dispersed in 50 mL of glacial acidic acid. After addition of 2.9 g (15 mmol) of 4-bromothiophenol, the mixture was heated to 75 °C for 5 h. The mixture was poured into water and the precipitate was isolated by centrifugation. After dissolving in ethyl acetate and drying over MgSO4, the solvent was removed. After washing with Et2O, the product was obtained as colorless solid in 60% yield.

1H-NMR (400 MHz, C6D6, 25 °C)

δ = 7.49 (m, 6H, H3), 6.99 (m, 6H, H2), 6.95 (m, 3H, H1), 6.84 (m, 2H, H5), 6.76 (m, 2H, H4) ppm.

13C-NMR (101 MHz, C6D6, 25 °C)

δ = 144.4 (C9), 136.0 (C4), 133.8 (C7), 131.3 (C5), 130.1 (C3), 127.9 (C2), 127.0 (C1), 122.3 (C6), 71.1(C6)

dissolved in C6D6 or 2-butanone. After addition of 1 equiv. of [Pd(P^tBu3)2], the reaction mixture was stirred at a temperature between room temperature and 70 °C, while monitoring the reaction by NMR spectroscopy.

7.2.10 Synthesis of 1,2-Bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)diphenyl disulfide²¹⁴

In a round bottom flask, 1.9 g (10 mmol) of 4-mercaptophenylboronic acid were dissolved in 100 mL of N,N-dimethylformamide and 1.4 mL of triethyl amine. Oxygen was bubbled through the solution for 1 h. After addition of water, the free boronic acid was isolated by extraction with Et2O.

The esterification with pinacol was performed by dissolving 1 equiv. of the disulfide and 2 equiv. of pinacol in THF/toluene (1:1 v/v ratio) and by removal of the solvent (three times) at a rotary evaporator at 40 °C water bath temperature. The desired product was obtained in quantitative yield.

1H-NMR (400 MHz, CDCl3, 25 °C)

δ = 7.71 (d, ³JHH = 8.3 Hz, 4H, H1), 7.47 (d, ³JHH = 8.3 Hz, 4H, H2), 1.32 (s, 24H, H3) ppm.

13C-NMR (101 MHz, CDCl3, 25 °C)

δ = 140.2 (C5), 135.6 (C1), 125.8 (C2), 83.9 (C4), 24.8 (C3) ppm. The carbon atom adjacent to the boron-moiety was not detected by ¹³C-NMR.