Hard-Soft Cooperativity of an Allosteric Tweezer.

Drawing inspiration from allosteric proteins, a zigzag-shaped π-conjugation was structurally engineered into a tweezer-like ionophore having multiple disparate binding sites. When a soft metal ion binds to the central tridentate ligand motif, the rigid backbone folds, bringing two macrocyclic arms into close proximity. Stabilized by a coordinating anion, the tweezer-like conformation of the resulting metalloligand recruits a hard cation to form a sandwich-like complex with a remarkably enhanced binding affinity and selectivity.

Sharp Turns and Fluorescent Repeats: Modular Construction and Shape-Dependent Electronic Properties of π-Conjugated Chain Molecules.

In search of the design rules for structural ordering of open-chain molecules, we have built a series of zig-zag shaped π-conjugated structures with ring-fused heteroaromatics as sharp turns and tolane-based linear fragments as light-emitting units. Using only a finite number of common building blocks, an efficient "double-elongation" strategy was implemented to construct a series of π-conjugated oligomers with precise length control (55-89 % yields). Our approach takes advantage of the modular nature of the bis(triazolo)benzene synthesis and the masked reactivity of the nitro group. A combination of photophysical and DFT computational studies revealed that the bis(triazolo)benzene-tolane repeat units behave as electronically decoupled light-absorbing/emitting units (λmax,em = 408-422 nm; ΦF = 20-25 % in THF). Such context-independent photophysical properties promise their potential applications in chemical sensing and switching.

Weak Links To Differentiate Weak Bonds: Size-Selective Response of π-Conjugated Macrocycle Gels to Ammonium Ions.

Molecular-level host-guest interactions can drive gel-to-sol phase transitions of the bulk material. Using supramolecular gels constructed from π-conjugated aza-crown macrocycles, we have investigated the effects of guest chemical structures on the kinetics of gel disassembly. While ammonium ions bind only weakly to the individual macrocycles in solution, gel-to-sol transitions of self-assembled macrocycles occur readily under ambient conditions. This net signal amplification process was monitored conveniently by time-dependent spectroscopic studies to reveal a straightforward correlation between the response rate and shape/size of the guest species. Well-designed weak links thus respond to subtle differences in weak bonds and translate them into visually discernible macroscopic signaling events.