Abstract
Efficient organic emitters in the deep-red to near infrared region are rare due to the ‘energy gap law’. Here, multiple boron (B)- and nitrogen (N)-atoms embedded polycyclic heteroaromatics featuring hybridized π-bonding/ non-bonding molecular orbitals are constructed, providing a way to overcome the above luminescent boundary. The introduction of B-phenyl-B and N-phenyl-N structures enhances the electronic coupling of those para-positioned atoms, forming restricted π-bonds on the phenyl-core for delocalized excited states and thus a narrow energy gap. The mutually ortho-positioned B- and N-atoms also induce a multiple resonance effect on the peripheral skeleton for the non-bonding orbitals, creating shallow potential energy surfaces to eliminate the high-frequency vibrational quenching. The corresponding deep-red emitters with peaks at 662 nm and 692 nm exhibit narrow full-width at half-maximums of 38 nm, high radiative decay rates of ~108 s-1, ~100% photo-luminance quantum yields and record-high maximum external quantum efficiencies of >28% in a normal planar organic light-emitting diode structure, simultaneously.