Dipyrrolyldiketone BF(2) complexes acting as acyclic anion receptors form supramolecular assemblies with structures and properties that are dependent on the pyrrole β-substituents. In particular, although β-alkyl substituents interfered with the formation of stable gel states, the introduction of fluorine moieties induced a stable supramolecular gel when compared to that of β-unsubstituted receptor.

Modified 3,5-dipyrrolylpyrazole (DPP) derivatives in their protonated form produce planar [2+2]-type complexes with trifluoroacetate (TFA) ions. These complexes serve as constituent components of ion-pair-based assemblies. An essential strategy for the construction of dimension-controlled organized structures based on these [2+2]-type complexes is the introduction of aryl rings bearing long alkyl chains, which enables the formation of 2D patterns at interfaces, supramolecular gels, and mesophases.

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.