Carboxylate‐Driven Supramolecular Assemblies of Protonated meso‐Aryl‐Substituted Dipyrrolylpyrazoles

Abstract

Dipyrrolylpyrazole (dpp) derivatives possessing an aryl ring at the pyrazole 4-position were synthesized. Upon protonation, modified dpp derivatives formed a variety of assembled structures through complexation with carboxylates, as observed by single-crystal X-ray and synchrotron XRD analyses. In particular, the complexation of protonated dpp species possessing long alkyl chains with dicarboxylates resulted in highly ordered assembled structures, the packing modes of which as lamellar structures were controlled by the lengths of the spacer units between two carboxylate moieties. The charge-carrier transporting properties of the solid materials were also controlled by bound anions, including dicarboxylates.

Ionic Liquid Crystals: Versatile Materials

“…280,359,548 Interestingly, while [C 12 C 12 im]-[NTf 2 ] does not show any enantiotropic LC phase (Table S2), 553,563 The Maeda group reported on protonated 3,5-dipyrrolylpyrazole derivatives (354-R 3 and 355) that form planar [2+2]-type ion-pair complexes with bridging [CF 3 COO] − anions through hydrogen bonding (Figure S21). 64,974 Compounds 354-R 3 (R 3 = H or F) show thermotropic columnar and cubic mesomorphism, and form supramolecular gels, as well as 2D patterns on a HOPG substrate. The hole mobility of 354-R 3 was measured in the solid state at room temperature by FP-TRMC, and it is higher than that of their nonprotonated precursors.…”