Jump to Main Content
Designing and Refining Ni(II)diimine Catalysts Toward the Controlled Synthesis of Electron-Deficient Conjugated Polymers
- Bridges, Colin
R., McCormick, Theresa M., Gibson, Gregory L., Hollinger, Jon, Seferos, Dwight S.
- Journal of the American Chemical Society 2013 v.135 no.35 pp. 13212-13219
- catalysts, electronics, nickel, polymerization, polymers, reaction kinetics, refining
- Electron-deficient π-conjugated polymers are important for organic electronics, yet the ability to polymerize electron-deficient monomers in a controlled manner is challenging. Here we show that Ni(II)diimine catalysts are well suited for the controlled polymerization of electron-deficient heterocycles. The relative stability of the calculated catalyst–monomer (or catalyst-chain end) complex directly influences the polymerization. When the complex is predicted to be most stable (139.2 kJ/mol), these catalysts display rapid reaction kinetics, leading to relatively low polydispersities (∼1.5), chain lengths that are controlled by monomer:catalyst ratio, controlled monomer consumption up to 60% conversion, linear chain length growth up to 40% conversion, and ‘living’ chain ends that can be readily extended by adding more monomer. These are desirable features that highlight the importance of catalyst design for the synthesis of new conjugated polymers.