In addition, the majority of previous attention has been paid to the tricoordinate boron units in PAHs, 10 tetracoordinate boron has been viewed more as a functional group instead of a dopant. In fact, the coordination number of boron atom shows noteworthy impact on the photophysical properties. Until recently, effort to replace the three-coordinate boron of BN unit with four-coordinate boron has been made (Scheme 1a). The formation/dissociation of four-coordinate boron unit through a dynamic B-N coordination bond in B-PAHs (A) has been exploited for the solution-processed fabrication of semiconducting films of poorly soluble B-PAHs. Hatakeyama et al reported that tetracoordinate boron-fused helicenes (B) as recently, Hatakeyama et al replaced the tricoordinate boron by tetracoordinate boron to form compound D. With respect to the synthetic methodology of introducing boron atoms, electrophilic borylation as the symbolic reaction to synthesize borylated compounds has shown advantages in efficiency, scalability and avoidance of previous reagents. However, this type of electrophilic borylation requires high temperature with high boiling point solvents, which needs long reaction time and makes subsequent purification difficult. We have longstanding interest both in developing synthetic methodology and applications of BN-doped PAHs. We have developed photo-driven elimination reactions to generate BN-PAHs and further expand this elimination using heat. We also proposed a new strategy named exciton-driven elimination (EDE) to enable the in situ solid-state conversion of nonemissive tetracoordinate boron-substituted heterocycles to highly emissive BN-PAHs in OLEDs. In addition, we recently demonstrated combination of electrophilic borylation and oxidative coupling to be a facile and viable approach to new NBN-doped molecular systems with tri-coordinate boron atoms (Scheme 1b). In this work, we further disclose the strategy of combining electrophilic borylation and oxidative coupling for producing tetra-coordinate boron-doped PAHs. Unlike the typical electrophilic borylation driven by high temperature, our system can quickly undergo borylation at room temperature followed by addition of different nucleophilic reagents to build tetra-coordinate BN-PAHs bearing different functional groups on boron atoms (Scheme 1c).