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N ‐Aryl‐9,10‐phenanthreneimines as Scaffolds for Exploring Noncovalent Interactions: A Structural and Computational Study
Author(s) -
Farrell David,
Kingston Samuel J.,
Tungulin Dmitry,
Nuzzo Stefano,
Twamley Brendan,
Platts James A.,
Baker Robert J.
Publication year - 2017
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201700884
Subject(s) - non covalent interactions , chemistry , steric effects , hydrogen bond , halogen bond , lone pair , stacking , aryl , crystallography , ligand (biochemistry) , stereochemistry , halogen , density functional theory , computational chemistry , molecule , organic chemistry , alkyl , receptor , biochemistry
A series of 10‐[(4‐halo‐2,6‐diisopropylphenyl)imino]phenanthren‐9‐ones and derivatives of the phenanthrene‐9,10‐dione ligand have been synthesised and structurally characterised to explore two types of noncovalent interactions, namely the influence of the steric bulk upon the resulting C–H ··· π and π‐stacking interactions and halogen bonding. Selected noncovalent interactions have additionally been analysed by DFT and AIM techniques. No halogen bonding has been observed in these systems, but X lone pair ··· π, C–H ··· O=C and C–H ··· π interactions are the prevalent ones in the halogenated systems. Removal of the steric bulk in N ‐(2,4,6‐trimethylphenyl)‐9,10‐iminophenanthrenequinone affords different noncovalent interactions, but the C–H ··· O=C hydrogen bonds are observed. Surprisingly, in N ‐(2,6‐dimethylphenyl)‐9,10‐iminophenanthrenequinone and N ‐(phenyl)‐9,10‐iminophenanthrenequinone these C–H ··· O=C hydrogen bonds are not observed. However, they are observed in the related 2,6‐di‐ tert ‐butylphenanthrene‐9,10‐dione. The π‐interactions in dimers extracted from the crystal structures have been analysed by DFT and AIM. Spectroscopic investigations are also presented and these show only small perturbations to the O=C–C=N fragment.