Abstract: | A pyrrole‐cleaving modification to transform boron(III) meso ‐triphenylsubporphyrin into boron(III) meso ‐triphenylsubchlorophin has been developed. Boron(III) subchlorophins thus synthesized show absorption and fluorescence spectra that are roughly similar to those of boron(III) subchlorins, but B ‐methoxy boron(III) subchlorophin showed considerably intensified fluorescence and a small Stokes shift. Peripheral modification reactions of B ‐phenyl boron(III) subchlorophin such as regioselective nitration with Cu(NO3)2⋅3 H2O, ipso ‐substitution reactions of boron(III) α‐nitrosubchlorophin with CsF and CsCl, and Pd‐catalyzed cross‐coupling reactions of boron(III) α‐chlorosubchlorophin with arylacetylenes, have been also explored to tune the optical properties of subchlorophins. |