Studies of photoreactive organoboron compounds have progressed rapidly in the last decade. This thesis reports on the discovery of new photochemical and photoluminescent properties of triaryl boron compounds and the attempt to synthesize pentacoordinate boron based \pi-conjugated systems with potential multi-responsive properties. In particular, we investigated the photoisomerization of boron-containing stilbene analogues and discovered a new multi-step photoisomerization process that leads to the formation of a rarely reported backbone containing three fused five-membered rings. This unusual reactivity was believed to be due to a special type of HOMO-LUMO interactions that are previously unknown in the literature. While the attempted synthesis of a series of new pentacoordinate boron compounds was unsuccessful, we presented in this thesis some preliminary results and discussed potential synthetic routes.