Benzothiazolyl hydrazones 1 (H₂L^PAH) incorporating polycyclic aromatic hydrocarbons (PAHs) have been fabricated as hemilabile scaffolds and elegantly utilized the inbuilt nitrogen donors as a proficient directing group (DG) to bring about ruthenium(II) assisted C–H activation in PAHs at both the peri and ortho positions. An isomeric pair of organometallics having formula [Ru^II(L^Pyr)(CO)(PPh₃)₂] (peri: 3a, ortho: 5a) have been conveniently prepared by varying the [Ru^II] precursors with H₂L^Pyr. In contrast, only one type of activated product viz. [Ru^II(L^Anc)(CO)(PPh₃)₂] 3b has been obtained with the 9-anthracene derivative of 1, H₂L^Anc, under analogous reaction conditions. The underlying mechanistic aspects have been elucidated by isolating the thermally unstable intermediates viz. [Ru^II(HL^Pyr)Cl(CO)(PPh₃)₂] 2a and [Ru^II(HL^Pyr)H(CO)(PPh₃)₂] 4a in the course of the peri and ortho C–H activation processes, respectively. The coligand (Cl/H) plays a vital role to bring about the C–H activation at the desired positions via formation of either a four- or five-membered metallacycle in 2a and 4a, respectively. The activation process vis-à-vis Ru–C bond formation in 3a can be achieved smoothly from 2a by a thermal transformation route, which proceeds via an initial rupture of the Ru–N_hydrazonyl bond. In contrast, the trans influential hydride coligand prefers a five-membered chelate to avoid confrontation with N_hydrazone in 4a, which in turn furnishes exclusively ortho activation owing to the close approach of the Ru–H bond towards ortho-H in pyrene. The organometallated complexes exhibit oxidative responses at mild potential. EPR and computational studies indicate that the redox activity originates from the ligand-centered orbitals. The observed rich optoelectronic features are analysed primarily as ¹ILCT admixed with ¹MLCT components by theoretical means, indicating an appreciable accumulation of electron density over the ligand backbone in their ground states.