A redox-active [ML] unit (M = Co-II and Mn-II; LH2 = N'-(1,4-dioxo-1,4-dihydronaphthalen-2-y1)benzohydrazide) defined as a cascade precursor that undergoes a multicomponent redox reaction comprising of a C-N bond formation, tautomerization, oxidation, C-C coupling, demetalation, and affording 6,14-dibenzoylbenzo[f]benzo [5,6] in dazolo [3a,3-c] indazole-5,8,13,16-tetraone (L-Ind(2)) is reported. Conversion of LH2 -> L-Ind(2) in air is overall a (6H(+)+6e) oxidation reaction, and it opens a route for the syntheses of bioactive diarylindazolo [3a,3-c]indazole derivatives. The reaction occurs via a radical coupling reaction, and the radical intermediate was isolated as a triphenylphosphonio adduct. In presence of PPh3 the [ML] unit promotes a reaction that involves a C-P bond formation, tautomerization, and oxidation to yield a stable zwitterionic triphenylphosphonio-hydrazyl radical (L-PPh3(+/-center dot)). Conversion of LH2 -> L-PPh3(+/-center dot) is a (3H(+)+3e) oxidation reaction. To authenticate the [ML], unit, in addition to the L-Ind(2) a zinc(II) complex, [(L-3)Zn-II(H2O)Cl]center dot 2Me0H (1.2MeOH), was successfully isolated (L3H = a pyridazine derivative of 1,4 naphthoquinone) from a reaction of LH2 with hydrated ZnCl2. Conversion of 3LH(2) -> 1 is also a multicomponent (6H(+)+6e) oxidation reaction promoted by zinc(II) ion via a radical intermediate. Facile oxidation of [L2-] to [L.-] that was considered as an intermediate of these conversions was confirmed by isolating a 1,4 naphthoquinone-benzhydrazyl radical (LH.) complex, [(LH center dot)Zn-II(H2O)Cl-2] (2H(center dot)). The intermediates of LH2 -> L-Ind(2), LH2 -> L-PPh3(+/-center dot), and 3LH(2) -> 1 conversions were analyzed by electrospray ionization mass spectroscopy. The molecular and electronic structures of L-PPh3(+/-center dot) (Ind)L2, 1.2MeOH, and 2H(center dot) were confirmed by single-crystal X-ray crystallography, electron paramagnetic resonance spectroscopy, and density functional theory calculations.