Herein, we report the synthesis of a series of push-pull imines by considering cyclic diamino substituent at the C-centre and fluoroaryl substituent at the N-centre. This has been achieved by a selective aromatic nucleophilic substitution of different fluoroarenes by N-H-substituted N-heterocyclic imines (NHIs) at ambient conditions without any additional reagent. Solid-state molecular structure analysis reveals the elongation of the central C-N bond of the imine functionality, which is consistent with the push-pull nature of these imines. The push-pull nature of these imines is further validated by computational studies.