To what extent can a conjugation between two pairs of peri‐nitro and peri‐amino groups be realized through the naphthalene core?

Abstract

Through‐conjugation for a wide range of 1,8‐diamino‐4,5‐dinitronaphthalenes (N‐acylated, N‐alkylated, N,N′‐bridged, N‐heterocyclic, and N‐deprotonated compounds) was for the first time quantified in solution by means of ultraviolet–visible and proton nuclear magnetic resonance spectroscopy and compared with that of the simpler naphthalene and benzene push‐pull systems. Surprisingly, an extent of conjugation in 1,8‐diamino‐4‐nitro‐ and 1,8‐diamino‐4,5‐dinitronaphthalenes measured in dimethyl sulfoxide is commensurable. On the whole, the repulsive peri‐interactions between the amino groups in systems with N‐alkylated and N‐deprotonated amino groups are more favorable for an effective D‐π‐A charge transfer than in N,N′‐bridged compounds (perimidines, 2,3‐dihydroperimidines and perimidin‐2‐ones). The best electron donors from peri‐positions are pyrrolidin‐1‐yl and methylamido groups. The conclusions obtained from solution studies were deepened by solid‐ state X‐ray experiments for a number of push–pull naphthalenes, including 6,7‐dinitroperimidine N‐anion and two representatives of 4,5‐diaminonaphthalene‐1,8‐dicarbaldehydes. In particular, they helped to trace changes in the bond order redistribution and twisting of the naphthalene core. The latter reaches a record value of 27° for 4,5‐dinitro‐1,8‐di(pyrrolidin‐1‐yl)naphthalene. Copyright © 2013 John Wiley & Sons, Ltd.