Unraveling the Push‐Pull Effect in Acenes, Polyenes and Polyynes

Abstract

Substituent effects (SEs) are fundamental for predicting molecular reactivity, while polyene, polyyne and acene derivatives are precursors to compounds with diverse applications. Computations were performed for Y‐R‐X systems, where reaction sites Y = NO2 and O−, substituents X = NO2, CN, Cl, H, OH, NH2, and spacers R = polyene, polyyne (n=1‐5, 10 repeating units) and acene (up to tetracene). The cSAR (charge of the substituent active region) approach allowed to present, for the first time, quantitative relations describing the spacer’s electron‐donating and withdrawing properties as a function of n and the spacer type. The electronic properties of the X substituents depend on the type of spacer, its length and the Y group, which is an example of the reverse SE. To describe how the SE between Y and X weakens with n, two approaches were compared: cSAR and SESE (SE stabilization energy). The EDDB (electron density of delocalized bonds) characterize changes in electron delocalization in spacers due to the SE. A new approach – EDDB differential maps – allow to extract the effect of X substitution on the electron delocalization. The charges at spacer’s C atoms correlate with cSAR; changes in the slopes confirm the charge transfer by resonance.