Computer-Guided Design of Photocatalyst for PET-RAFT Polymerisation

In recent years, the use of photocatalysts (PCs) has found a broad range of applications in polymer synthesis, especially in precise temporal/spatial control, precise sequence control, selective and orthogonal polymerisation systems. The new discovery of PCs for photo-controlled reversible deactivation radical polymerisation (photo-RDRP) was generally performed using an experimental approach, where various PCs were tested. However, the experimental approach requires laborious synthesis work and lack efficiency. With the development of new computational tools, a rational design approach has emerged, which can allow a rapid discovery of new PCs. How the modification of substituents in the PCs affects their different properties (absorption, absorbance, redox-potential of excited states, quantum yields) can rapidly been uncovered by the aid of computation. Thereby, using large libraries of synthesized PCs, it is possible to establish correlations between structures and photocatalytic activities and guide design of new PCs. In this thesis, we pioneered fully computer-guided discoveries of new functional PCs for photo-RDRP mechanisms by firstly developing and investigating the design guidelines and then integrate the most state-of-art computational techniques to enable systematic methodologies of fully computer-guided design of PCs for photo-RDRP for the first time.