1. Organocatalyzed atom transfer radical polymerization driven by visible light
by Jordan C. Theriot, Chern-Hooi Lim, Haishen Yang, Matthew D. Ryan, Charles B. Musgrave, and Garret M. Miyake
Science
Volume 352(6289):
May 27, 2016
Published by AAAS

2. Fig. 1 PC development for O-ATRP.
PC development for O-ATRP. (A) Polymerization of MMA to well-defined polymers by using photoredox O-ATRP driven by sunlight. (B) Structures of the diphenyl dihydrophenazine PCs 1 to 4 used in this study. (C) A proposed mechanism for ATRP mediated by a PC via photoexcitation to 1PC*, intersystem crossing (ISC) to the triplet state 3PC*, ET to form the radical cation doublet 2PC•+, and back ET to regenerate PC and reversibly terminate polymerization.
Jordan C. Theriot et al. Science 2016;352:
Published by AAAS

3. Fig. 2 Polymerization results using PC 3.
Polymerization results using PC 3. (A) Plot of molecular weight as a function of monomer conversion and (B) plot of dispersity as a function of monomer conversion for the polymerization of MMA mediated by 3. (C) Chain-extension from a PMMA macro-initiator (black) to produce block copolymers with MMA (green), BMA (blue), and BA (red). (D) GPC traces of each polymer depicted in (C) (color coded).
Jordan C. Theriot et al. Science 2016;352:
Published by AAAS

4. Fig. 3 Calculated triplet state (3PC
Fig. 3 Calculated triplet state (3PC*) frontier orbitals and excited-state reduction potentials E0* of diphenyl dihydrophenazine PCs 1 to 4.
Calculated triplet state (3PC*) frontier orbitals and excited-state reduction potentials E0* of diphenyl dihydrophenazine PCs 1 to 4. (Top) The higher-lying SOMO. (Bottom) The low-lying SOMO. Phenyl functionalization with electron-withdrawing groups (CF3 and CN) localizes the high-lying SOMO on the phenyl.
Jordan C. Theriot et al. Science 2016;352:
Published by AAAS

5. Fig. 4 Computationally directed discovery of PCs 5 and 6.
Computationally directed discovery of PCs 5 and 6. (A) Structures of 5 and 6 and the calculated E0*. (B) Triplet-state frontier orbitals of 5 and 6 showing the (top) higher-lying SOMO and (bottom) low-lying SOMO.
Jordan C. Theriot et al. Science 2016;352:
Published by AAAS

6. Fig. 5 Results for the polymerization of MMA using PC 6.
Results for the polymerization of MMA using PC 6. (A) Plot of Mn and Đ versus monomer conversion for the polymerization of MMA under continuous irradiation. (B) Plot of monomer conversion versus time and (C) plot of Mn and Đ (solid symbols indicate after irradiation, and open symbols indicate after dark period) versus monomer conversion, using 6 as the PC during pulsed light irradiation with white LEDs. Experimental details are provided in the supplementary materials.
Jordan C. Theriot et al. Science 2016;352:
Published by AAAS