Thieno-fused subporphyrazines (TPs) containing a central and axially substituted boron atom are a class of compounds with interesting optical and redox properties. Here we present our efforts towards expanding this class of compounds using various thiophene substrates that were prepared by cyanation or nitration of 3,4-dibromothiophene. Moreover, we show that one TP derivative forms a 2:1 complex in the solid state with C70.