beta-to-o-phenyl doubly fused porphyrins (DFPs) or chlorins (DFCs) were selectively synthesized by facile oxidative fusion of trans-chlorins using 2,3-dichloro-5,6-dicyano1,4-benzoquinone (DDQ) in good-to-excellent yields (70-92%) under mild reaction conditions with high atom economy. The selectivity in product formation (difused porphyrin or chlorin) was controlled by the presence or absence of a Ni(II) ion in the macrocyclic core. Notably, nickel(II) trans-chlorins selectively yielded DFPs, whereas free-base trans-chlorins afforded only DFCs. The synthesized fused porphyrinoids exhibited significantly red-shifted electronic spectral features (Delta lambda(max) = 16-53 nm) of the Soret band due to the extended pi conjugation and highly twisted macrocyclic conformation (twist angle similar to 20-34 degrees). Inner-core NHs of fused chlorins exhibited a tremendous downfield shift (Delta delta = 1.71-2.02 ppm) compared to their precursors. The overall protonation constants for indanedione-substituted free-base-difused chlorins (4-6) were profoundly higher (similar to 20-50-fold) compared to dicyanomethyl-appended free-base-difused chlorins (10-12) because of the combined effect of the electronic nature of the beta-substituents and nonplanarity of the macrocyclic core. The first oxidation potential of H2DFC(MN)(2)Ph-2 (12) was 0.54 V cathodically shifted with respect to H2DFC(MN)(2) (10) because of the electron-donating nature of the beta-phenyl groups, which resulted in extensive destabilization of the highest occupied molecular orbital.