Introduction of a BINOL-boron moiety to dipyrrolyldiketones as precursors of anion-responsive π-conjugated molecules results in the formation of a chiral environment in the form of anion-free receptors and anion-binding complexes. Conformation changes by inversion (flipping) of two pyrrole rings as a result of anion binding can control the chiroptical properties of the anion receptors. In particular, appropriate pyrrole β-substituents induce distorted receptor π-planes and, as a result, give larger circularly polarized luminescence (CPL), which can be tuned by chemical stimuli (anions). This is the first example of chemical-stimuli-responsive CPL properties.

This short review article summarizes recent progress in research on various stimuli-responsive circularly polarized luminescence (CPL) properties derived from π-conjugated molecules and related materials. As representative examples, assembled structures of chiral π-conjugated polymers and molecules showed tunable CPL resulting from the enhancement of chirality induction by aggregation. Fascinating CPL-active species, pyrrole-based anionresponsive π-conjugated molecules exhibiting CPL induced by anion binding and ion pairing, are also discussed.

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Pentacyanocyclopentadienide (PCCp(-) ), a stable π-electronic anion, provided various ion-pairing assemblies in combination with various cations. PCCp(-) -based assemblies exist as single crystals and mesophases owing to interionic interactions with π-electronic and aliphatic cations with a variety of geometries, substituents, and electronic structures. Single-crystal X-ray analysis revealed that PCCp(-) formed cation-dependent arrangements with contributions from charge-by-charge and charge-segregated assembly modes for ion pairs with π-electronic and aliphatic cations, respectively. Furthermore, some aliphatic cations gave dimension-controlled organized structures with PCCp(-) , as observed in the mesophases, for which synchrotron XRD analysis suggested the formation of charge-segregated modes. Noncontact evaluation of conductivity for (C12 H25 )3 MeN(+) ⋅PCCp(-) films revealed potential hole-transporting properties, yielding a local-scale hole mobility of 0.4 cm(2)  V(-1)  s(-1) at semiconductor-insulator interfaces.

Summary Porphyrin–Au III complexes were found to act as π-electronic cations, which can combine with various counteranions, including π-electronic anions. Single-crystal X-ray analyses revealed the formation of assemblies with contributions of charge-by-charge and charge-segregated assemblies, depending on the geometry and electronic state of the counteranions. Porphyrin–Au III complexes possessing aliphatic alkyl chains formed dimension-controlled ion-pairing assemblies as thermotropic liquid crystals, whose ionic components were highly organized by π–π stacking and electrostatic interactions.