Extreme enhancement of secondary chirality through coordination-driven steric changes of terpyridyl ligand in...

Aggregation-induced chirality is potentially useful in sensor technology applications. Herein we show extreme enhancement of secondary chirality through coordination-driven steric changes of terpyridyl ligand in molecular gels. The secondary chirality reflecting on enhancement of chiral signals (i.e., circular dichroism (CD) and circularly polarised luminescence (CPL)) of the molecular gels formed from glutamide-attached terpyridine (G-tpy) is extremely enhanced by the coordination of its terpyridyl groups to metal ions such as Cu²⁺, Zn²⁺ and Ru²⁺, which is due to dramatic changes in the stacked structure of the chromophore groups through the formation of metal ion complex. Metal-free terpyridine exists in a non-planar geometry, which suppress π-π stacking interactions among aggregates. The planarity of the terpyridyl group is improved through metal-ion complexation, which induces the metal-ion-coordinated terpyridyl groups to stack. The thermal stabilities of the CD signals are strongly affected by the metal-ion species. CPL signal is generated in the molecular gel formed from G-tpy-Zn²⁺ complex accompanied by chelation-enhanced fluorescence. It is expected that large and sensitive coordination-driven secondary chirality signals (CD and CPL) are useful for sensing guest molecules and the surrounding environment.