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Computation and

Photocatalyst Design

The performence of photoredox reactions (e.g. PET-RAFT polymerisation) are controlled through a structure-property-performance relationship of the photocatalyst (PC).

Rational design or modification of the chromophore core structure and its substituted ligands leads to variation of photophysical properties (i.e. absorption wavelengths, molar absorptivity, quantum yields, excited states lifetimes, nature of molecular orbitals etc.) and electrochemical properties.

By tailoring properties of PC by structrual design, the performace of photoredox reactions can be controlled.


Based on this knowledge, we adopted a fully computer-guided strategy in discovering an efficient pHswitchable organic photocatalyst (OPC), unprecedentedly turning colorless at pH 5 and recovering strong visible-light absorption and photoactivity at pH 7. This is the first example of an OPC design fully guided by comprehensive density functional theory (DFT) studies covering electrostatic, electrochemical, and photophysical predictions. Characterization of the designed OPC after synthesis confirmed the computational predictions. We applied this OPC to mediate an aqueous photoinduced electron/energy transfer - reversible addition fragmentation chain transfer (PET-RAFT) polymerization under green LED light (nominal emission wavelength: 530 nm, 5 mW/cm2 ). We demonstrated that the polymerization can be reversibly ceased by a slight change of pH (pH ≤ 5.0) or in the absence of light. Furthermore, we demonstrated that the polymerization rate could be significantly retarded by bubbling carbon dioxide into the reaction solution under visible light. Conversely, the rate could be fully recovered via exposure to nitrogen gas. This is the first example of a pH and light dual-gated polymerization system with complete and reversible inhibition.


Related publications

  • Wu, C.;  Jung, K.;  Ma, Y.;  Liu, W.; Boyer, C., Unravelling an oxygen-mediated reductive quenching pathway for photopolymerisation under long wavelengths. Nature Communications 2021, 12 (1), 478. Read More​

  • Wu, C.; Chen, H.; Corrigan, N.; Jung, K.; Kan, X.; Li, Z.; Liu, W.; Xu, J.; Boyer, C., Computer-Guided Discovery of a pH-Responsive Organic Photocatalyst and Application for pH and Light Dual-Gated Polymerization. Journal of the American Chemical Society 2019, 10.1021/jacs.9b01096. Read More​

  • Seal, P.; Xu, J.; Luca, S. D.; Boyer, C.; Smith, S. C., Unraveling Photocatalytic Mechanism and Selectivity in PET‐RAFT Polymerization. Advanced Theory and Simulations 2019, 10.1002/adts.201900038. Read More

  • Corrigan, N; Xu, J.; Boyer, C,; Allonas, X., Exploration of the PET‐RAFT Initiation Mechanism for Two Commonly Used Photocatalysts, ChemPhotoChem 2019, 10.1002/cptc.201800182. Read More

  • Wu, C., Corrigan, N., Lim, C.H., Jung, K., Zhu, J., Miyake, G., Xu, J. and Boyer, C., 2018. Guiding the Design of Organic Photocatalyst for PET-RAFT Polymerization: Halogenated Xanthene Dyes. Macromolecules 2018, 52 (1), 236-248. Read More​

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