An efficient room-temperature synthesis of highly phosphorescent styrenic Pt(ii) complexes and their polymerization by ATRP

Abstract

Cyclometalated Pt(II) complexes are among the most efficient phosphorescent materials, yet their incorporation into polymers remains rare. This is largely due to challenges with existing synthetic methods, characterized by long reaction times, excess reagents, high temperatures and low product yields. Here we demonstrate a stoichiometric, one-pot cyclometalation protocol which gives Pt-containing styrenic monomers in short reaction times at ambient temperature with improved yields. These monomers were then incorporated into highly phosphorescent polymers by ATRP, giving materials with M_n ∼ 10 000 and Đ = 1.12–1.15. The preparation of block copolymers is also demonstrated, as well as the synthesis of mixed-colour phosphorescent films using partial energy transfer between platinum chromophores. This cyclometalation protocol should make the preparation of Pt(II) metallopolymers significantly more accessible, opening the door to a broad range of applications in optoelectronics.