Photophysical, spectroscopic and chromatographic dataset for Hydrophobic and Hydrophilic Ag-In-Zn-S Alloyed Quantum Dots as Efficient Photocatalysts for Controlled RAFT Polymerization of Vinyl Monomers

Description (1) Elemental analysis of alloyed Ag-In-Zn-S quantum dots was carried out with a multichannel Quantax 400 energy-dispersive X-ray spectroscopy (EDS) system with a 125 eV xFlash detector 5010 (Bruker) using a 15 kV electron beam energy. (2) High-resolution images were acquired by a Tecnai TF20 X-TWIN (Thermo Fisher Scientific) microscope operated at 200 kV. (3) X-ray powder diffractograms were recorded at room temperature on a Bruker D8 Advance diffractometer equipped with a LYNXEYE position-sensitive detector using Cu Ka radiation (l = 0.15418 nm). The data were collected in the Bragg-Brentano (q/2q) horizontal geometry (flat reflection mode) between 10° and 70° (2q) in a continuous scan, using 0.04° steps at 960 s/step. The incident-beam path in the diffractometer was equipped with a 2.5° Soller slit and a 1.14° fixed divergence slit, whereas the path of the diffracted beam was equipped with a programmable antiscatter slit (fixed at 2.20°), a Ni b-filter, and a 2.5° Soller slit. The sample holder was rotated at an angular speed of 15 rpm. The data were collected under standard conditions (temperature and relative humidity). (4) UV-vis-NIR spectra were registered using a Cary 5000 (Varian) spectrometer. (5) Steady-state PL spectra of toluene solutions of samples were measured with FLS-980 fluorescence spectrophotometer equipped with a 450 W Xe lamp and photomultiplier (Hamamatsu, R928P) detector with a standard 10 mm cuvette (λexc = 375 nm). (6) The PL lifetime measurement was performed with a time correlated single photon counting (TCSPC) method on FLS-980 fluorescence spectrophotometer. The excitation wavelength (405 nm) was obtained using the picosecond pulsed diode laser (EPL - 405 nm, Edinburgh Instruments). (7) The number-average molar mass (Mn) and the molecular weight distribution (Ð) of the samples were determined by Size Exclusion Chromatography (SEC). The system was composed of a Viscotek GPCmax unit (pumping and degassing of solvent, sample injection with autosampler), a 305TDA detection unit (consisting of column, a UV measuring cell, RI detector, hybrid Right-Angle Light Scattering/Low-Angle Light Scattering (RALS/LALS) detector, and a viscometer), and a PDA UV detector (190-500 nm). The system was equipped with a Jordi Labs DVB column (mixed bed, 5 mm), which worked with dichloromethane at 30 °C, with a flow rate of 1 cm3/min. (8) The MALDI-ToF mass spectra were recorded on a Bruker UltraFlex (Bremen, Germany) spectrometer using trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB) as a matrix and analyzed with flexAnalysis v.3.3 (Bruker Daltonik GmbH) and Polymerix v. 2.0 (Sierra Analytics Inc.) software. The solutions for MALDI-ToF analyses were prepared by dissolving 5 mg of the sample in 1 mL of methylene chloride. (9) 1H and 13C NMR spectra were recorded on a Bruker Avance (400 MHz) spectrometer and referenced with respect to tetramethylsilane (TMS) and solvents. (10) Electron paramagnetic resonance (EPR) spectra were obtained with a Bruker EMX EPR spectrometer (Bruker-Biospin, Germany) operating at the X-band frequency (9.7 GHz) at room temperature. Typical instrument parameters were as follows: central field, 3480 G; modulation amplitude, 1.0 G; gain, 4.48×104 G; microwave power, 31.81 mW; sweep width, 100 G. References (1) Energy-dispersive spectra of alloyed Ag1.0In1.5Zn0.3S3.3 (R), Ag1.0In1.3Zn0.5S3.3 (R-MUA), Ag1.0In10.3Zn12.4S11.8 (G) and Ag1.0In2.7Zn30.0S90.0 (G-MUA) quantum dots. (2) HR-TEM images of alloyed Ag1.0In1.5Zn0.3S3.3 (R), Ag1.0In1.3Zn0.5S3.3 (R-MUA), Ag1.0In10.3Zn12.4S11.8 (G) and Ag1.0In2.7Zn30.0S90.0 (G-MUA) quantum dots. (3) X-ray powder diffractograms of alloyed Ag1.0In1.5Zn0.3S3.3 (R) and Ag1.0In10.3Zn12.4S11.8 (G) quantum dots. (4) UV-vis-NIR spectra of toluene (water) dispersion of R (R-MUA) and G (G-MUA) alloyed Ag-In-Zn-S quantum dots and Ru(bpy)32+. (5) Photoluminescence excitation and emission spectra of toluene (water) dispersion of R (R-MUA) and G (G-MUA) quantum dots. (6) Photoluminescence decay curves of toluene (water) dispersion of R (R-MUA) and G (G-MUA) quantum dots. (7) SEC profiles of PMMA, PDMA and PMMA-b-PBnMA prepared in bulk and solution polymerization. (8) MALDI-TOF spectra in the low molecular weight ranges of PMMA and PDMA synthesized in the presence of Ag1.0In1.5Zn0.3S3.3 (R) and Ag1.0In10.3Zn12.4S11.8 (G) quantum dots as photocatalysts. (9) 1H and 13C NMR spectra (in benzene-d6 or CDCl3) of the reaction mixture used for the photocatalytic bulk and solution polymerization of methyl methacrylate (MMA) and N,N-dimethylacrylamide (DMA) with Ru(bpy)32+ and Ag1.0In1.5Zn0.3S3.3 (R) and Ag1.0In10.3Zn12.4S11.8 (G) quantum dots as a photocatalyst. (10) DMPO spin-trapping EPR spectra of toluene dispersion of Ag1.0In1.5Zn0.3S3.3 (R), Ag1.0In10.3Zn12.4S11.8 (G) quantum dots and reaction mixture used for the photocatalytic polymerization of MMA.