Hydrogen-bond-assisted supramolecular 1-D tape-like structures of mesogenic bis-pyrazoles

Two new series of isomeric bis-pyrazoles 1a-b are prepared, characterized, and their mesomorphic properties investigated. These pyrazoyl derivatives were obtained from the condensation of alpha,beta-diketones 2a-b with hydrazine monohydrate in refluxing THF. Two single crystallographic structures of compounds mesogenic 1a (n = 14) and nonmesogenic 1b (n = 8) were determined by X-ray analysis. Both 1a-14 and 1b-8 crystallize in a triclinic space group P-1 and monoclinic C2/c group, respectively. An extended H-bonded structure was formed in both crystal lattices, giving a pseudo 1D-polymeric tape-like structure. Derivatives 1a exhibited smectic A/C mesophases, in contrast, derivatives 1b were all nonmesogenic. The difference in mesomorphic behavior was attributed to the between linear conformation and the coplanarity of the five rings over than in 1a. The correlation between the molecular structures and the mesomorphic properties is discussed. (C) 2012 Elsevier Ltd. All rights reserved.