Hydrogen-bonded tapes based on symmetrically substituted diketopiperazines: A robust structural motif for the engineering of molecular solids - CEA - Commissariat à l’énergie atomique et aux énergies alternatives Accéder directement au contenu
Article Dans Une Revue Journal of the American Chemical Society Année : 1997

Hydrogen-bonded tapes based on symmetrically substituted diketopiperazines: A robust structural motif for the engineering of molecular solids

Résumé

A series of eight symmetrically substituted diketopiperazines (DKPs) derived from 1-amino-1-carboxycycloalkanes (n = 3−7; 3,3,5,5-tetramethylcyclohexane; 4,4-dimethylcyclohexane; 2-indan) were synthesized and their crystal structures determined. In the solid state, all eight compounds form two pairs of hydrogen bonds with two adjacent molecules to form a one-dimensional structure that we refer to as "tapes". These molecules represent a range of volumes and shapes that contain a common molecular fragment (DKP ring). We examined this series of compounds with three objectives in mind: (i) to establish the ability of the hydrogen-bonded "tape" motif to persist through these differences in volume and shape; (ii) to provide a series of structurally related compounds to use to test computational methods of predicting crystal structure from molecular structure; (iii) to search for qualitative correlations between molecular structure and crystal packing. All compounds form tapes and with one exception, all tapes pack with their long axes parallel. When viewed down their long axis, two types of tapes emerge: planar and nonplanar. The type of tape that forms reflects the conformation adapted by the DKP ringplanar or boat. Planar tapes form when the angle (α) between the two planes defined by the cis-amides in the DKP ring is 180°; nonplanar tapes form when α < 180°. Five of the eight compounds studied form planar tapes, the remaining three compounds form nonplanar tapes. Despite the variability in volume and shape represented by this series of molecules, the persistence of the tape motif in their crystalline solids suggests that the hydrogen-bonding interactions between DKPs dominate the packing arrangement of these molecules. Void space in the crystalline solid is minimized by parallel alignment of tapes that pack in a manner that permits the interdigitation of substituents on adjacent tapes.

Domaines

Matériaux

Dates et versions

cea-01057083 , version 1 (21-08-2014)

Identifiants

Citer

Serge Palacin, Donovan N. Chin, Eric E. Simanek, John C. Macdonald, George M. Whitesides, et al.. Hydrogen-bonded tapes based on symmetrically substituted diketopiperazines: A robust structural motif for the engineering of molecular solids. Journal of the American Chemical Society, 1997, 119, pp.11807-11816. ⟨10.1021/ja962905b⟩. ⟨cea-01057083⟩

Collections

CEA CNRS IRAMIS
40 Consultations
0 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More