Phosphorescent organic light-emitting devices (OLEDs) have attracted increased attention from both academic and industrial communities due to their potential practical application in high-resolution full-color displays and energy-saving solid-state lightings. The performance of phosphorescent OLEDs is mainly limited by the phosphorescent transition metal complexes (such as iridium(III), platinum(II), gold(III), ruthenium(II), copper(I) and osmium(II) complexes, etc.) which can play a crucial role in furnishing efficient energy transfer, balanced charge injection/transporting character and high quantum efficiency in the devices. It has been shown that functionalized main-group element (such as boron, silicon, nitrogen, phosphorus, oxygen, sulfur and fluorine, etc.) moieties can be incorporated into phosphorescent emitters and their host materials to tune their triplet energies, frontier molecular orbital energies, charge injection/transporting behavior, photophysical properties and thermal stability and hence bring about highly efficient phosphorescent OLEDs. So, in this review, the recent advances in the phosphorescent emitters and their host materials functionalized with various main-group moieties will be introduced from the point of view of their structure–property relationship. The main emphasis lies on the important role played by the main-group element groups in addressing the key issues of both phosphorescent emitters and their host materials to fulfill high-performance phosphorescent OLEDs.

Organic light-emitting diodes (OLEDs) show great promise of revolutionizing display technologies in the scientific community. One successful approach for improved device efficiency has been to maximize the electron-hole recombination using dopants that emit from the triplet excited state. In this context, heavy transition metal complexes have recently gained tremendous academic and industrial research interest for fabricating highly efficient phosphorescent OLEDs by taking advantage of the 1:3 exciton singlet/triplet ratio predicted by simple spin statistics. Traditional room-temperature phosphorescent dyes are monofunctional materials working only as light-emitting centres but other key issues including charge generation and transport remain to be addressed in the electroluminescence. This Feature Article highlights recent and current advances in developing new synthetic strategies for multifunctional organometallic phosphors, which integrate both luminescent and charge carrier injection/transport functions into the same molecules so that they perform most, if not all, of the necessary functional roles (viz. photoexcitation, charge injection and transport as well as recombination) for achieving high-efficiency devices. Considerable focus is placed on the design concepts towards the tuning capability of charge-transport characteristics and phosphorescence emission colour of this prominent class of metallophosphors. In particular, the latest research endeavor in accomplishing novel triplet emitters with enhanced charge injection/charge transport of both hole and electron carriers is criticially discussed, which can provide good implications regarding their possible routes for future research development in the field.