Tetrabenzotriazacorroles (Tbcs) are a family of molecules related to phthalocyanines but have the unique ability to intensely absorb both blue and red light. Here, we report the synthesis of four novel silicon tetrabenzotriazacorrole derivatives (SiTbcs) with varying sized axial ligands. SiTbcs are formed starting from bis(hydroxy) silicon phthalocyanine ((OH)(2)-SiPc) via a simple in situ axial functionalization and reductive chemical process using magnesium metal and the respective chlorosilane in pyridine. Systematic probing of the reaction conditions revealed that the reaction is acid-promoted and that the formation of the Tbc macrocycle occurs at temperatures as low as 40 degrees C. Results imply this chemistry can be extended to SiTbcs with any axial ligands using pyridine hydrochloride as an acid source. Single crystals of all compounds were grown and showed significant pi-pi it interactions between the macrocycles in the solid state. Optical, electrochemical, and thermal characterization of these materials is also described. The SiTbcs exhibit interesting highly oxidative electrochemistry as well as high thermal stability and tunable phase transition behavior.