In addition to the prevalent atoms that contribute lone pair electrons to form 8π structures within hexacyclic rings, there exist uncommon tetrahedral atoms that participate in the construction of Baird aromatic rings. Accordingly, the subsequent reported molecules exhibit typical Baird-driven aromaticity reversal and luminescence enhancement resulting from conformational constraints, serving as maverick but compelling instances of specialized heterocyclic evidence that substantiates a deeper elucidation of the planarized conversion mechanism. We postulate that the inherent rigidity of planarized conversion molecules may perturb the proportion between planar and non-planar conformers in the excited states. The impetus from Baird aromaticity and the influenced vibrational constraint from the molecules' milieu counterbalance each other, thereby modulating emission band intensities corresponding to the two disparate configurations. For the more flexible and diminutive molecules , their rapid conformational invertibility (within picoseconds) results in non-radiative decay, precluding long wavelength fluorescence of planar structure in solution state. Reproduced from Ref. with permission. Copyright (2020), American Chemical Society. (d) PDBA molecule with irreversible photoinduced flipping and PTBA molecule with reversible photoinduced flipping, featuring a centrally highlighted ring that complies with Baird's rule for 8π electron structures. (e) Temperature dependence of PTBA emission spectra in methylcyclohexane ranging from 278 K to 358 K. (f) Irreversible and reversible aromaticity-driven photoinduced planarization kinetics. Reproduced from Ref. with permission. Copyright (2022), American Chemical Society.