DOI: 10.5281/zenodo.10887534
title: Photophysical and Spectroscopic dataset for Ag-In-Zn-S alloyed nanocrystals as photocatalysts of controlled light-mediated radical polymerization

description: (1) Energy-dispersive spectra of alloyed Ag1.0In1.5Zn0.3S3.3 (R)  and Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals.

(2) HR-TEM images of alloyed Ag1.0In1.5Zn0.3S3.3 (R)  and  Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals.

(3) X-ray powder diffractograms of alloyed Ag1.0In1.5Zn0.3S3.3 (R)  and  Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals.

(4) UV-vis-NIR spectra of toluene dispersion of Ag1.0In1.5Zn0.3S3.3 (R)  Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals.

(5) Photoluminescence excitation and emission spectra of toluene dispersion of Ag1.0In1.5Zn0.3S3.3 (R) and  Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals.

(6) 1H and 13C NMR spectra (in benzene-d6) of the reaction mixture used for the photocatalytic bulk and solution polymerization of methyl methacrylate (MMA) with Ag1.0In1.5Zn0.3S3.3 (R) and Ag1.0In10.3Zn12.4S11.8 (G)  nanocrystals as a photocatalyst.

(7) SEC profiles of PMMA prepared in bulk and solution polymerization.

(8) MALDI-TOF spectra in the low and high molecular weight ranges of PMMA synthesized in the presence of Ag1.0In1.5Zn0.3S3.3 (R) and Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals as photocatalysts.

(9) EPR spectra of adducts generated for Ag1.0In1.5Zn0.3S3.3 (R) and Ag1.0In10.3Zn12.4S11.8 (G) nanocrystals + 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) under illumination by a green LED (l = 523 nm).

This work was supported by the National Science Centre of Poland, Grant No. 2022/45/B/ST5/02120
description: Materials. Silver nitrate (99%), indium(II) chloride (99%), zinc stearate (technical grade), 1- dodecanethiol (DDT, 98%), sulfur (99%), 1-octadecene (ODE, 90%), oleylamine (OLA, 70%), methyl methacrylate (MMA, 99%), trietylamine (Et3N, 99.5%), methyl α-bromophenylacetate (MBP, 97%), 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid (CPADB) and benzene-d6 (100%, 99.6 atom % D) were supplied by Sigma-Aldrich (Merck KGaA, Darmstadt, Germany).

Preparation of the S/OLA Precursor. Sulfur powder (15 mg, 0.47 mmol) and OLA (1.0 mL) were loaded into a glass vial, which was then immersed in an ultrasonic bath. The mixture was sonicated at room temperature (for about 10 min) until a clear red solution was formed.

Preparation of Ag-In-Zn-S Nanocrystals (Red and Green). All operations were carried out under a constant dry argon flow. Silver nitrate (0.03 g, 0.18 mmol), indium(II) chloride (0.11 g, 0.59 mmol), DDT (0.20 g, 1.0 mmol), and zinc stearate (0.11 g, 0.18 mmol for R or 1.10 g, 1.62 mmol for G) were mixed with ODE (15 mL) in a three-neck flask. The mixture was heated to 150 °C until a homogeneous solution was formed. Then, 1 mL of the S/OLA precursor was quickly injected into the reaction solution. The temperature was increased to 180 °C, and the mixture was kept at this temperature for 60 min. After the mixture was cooled to room temperature, toluene (10 mL) was added, and the reaction mixture was centrifuged; the isolated black precipitate consisting of organic waste and agglomerated particles was separated. The supernatant was treated with 30 mL of acetone, leading to the precipitation of the desired fraction of nanocrystals. The nanocrystals were separated by centrifugation (7000 rpm, 5 min) and then redispersed in benzene-d6.

Procedures for the Bulk Photopolymerization of Methyl Methacrylate. To a mixture of methyl methacrylate (8 mL), trietylamine (0.13 mL, 0.96 mmol) and methyl α- bromophenylacetate (0.1 mL, 0.60 mmol) was added Ag1.0In1.5Zn0.3S3.3 (R) (~1.4 mg in 0.1 mL of benzene-d6) or Ag1.0In10.3Zn12.4S11.8 (G) (2.1 mg in 0.1 mL of benzene-d6). The vial was sealed and purged with argon for 10 min before illumination by either ultraviolet (8 x 5.6 W LEDs, λ = 365 nm) or blue (16 x 4.3 W LEDs, λ = 457 nm) or green (16 x 16.4 W LEDs, λ = 523 nm) light using THALESNano photoreactor. After stirring at room temperature for 6 h, a small amount of the reaction mixture (0.1 mL) was diluted in benzene-d6 or dichloromethane (0.5 mL) and analyzed via NMR spectroscopy or GPC respectively.

Procedure for the Solution Photopolymerization of Methyl Methacrylate. To a solution of methyl methacrylate (8 mL), trietylamine (0.13 mL, 0.96 mmol) and methyl α- bromophenylacetate (0.1 mL, 0.60 mmol) in benzene-d6 (8 mL) was added Ag1.0In1.5Zn0.3S3.3 (R) (~1.4 mg in 0.1 mL of benzene-d6) or Ag1.0In10.3Zn12.4S11.8 (G) (2.1 mg in 0.1 mL of benzene-d6). The vial was sealed and purged with argon for 10 min before illumination by either blue (16 x 4.3 W LEDs, λ = 457 nm) light using THALESNano photoreactor. After stirring at room temperature for 1, 2, 3, 4 and 5 h, a small amount of the reaction mixture (0.1 mL) was diluted in benzene-d6 or dichloromethane (0.5 mL) and analyzed via NMR spectroscopy or GPC respectively.
description: (1) Elemental analysis of alloyed Ag-In-Zn-S nanocrystals 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) 1H and 13C NMR spectra were recorded on a Bruker Avance (400 MHz) spectrometer and referenced with respect to tetramethylsilane (TMS) and solvents.

(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) 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.