Background: Benzoxazole-containing ligands find many applications both in medicinal chemistry, catalysis and fluorescence chemosensing. Benzoxazole-containing macrocycles could be therefore a good strategy to achieve stable and selective fluorescent complexes with suitable metal ions. In this work, the synthesis, binding, and photochemical properties of a new fluorescent ligand (L) are reported. L is a cyclophane macrocycle containing the 1,3-bis(benzo[d]oxazol-2-yl)phenyl (BBzB) fluorophore and an aliphatic tetra-amine chain to form the macrocyclic skeleton. Methods: Spectrophotometric and spectrofluorimetric measurements, ¹H NMR analysis, and DFT calculations were performed. Results: L behaves as a PET-mediated chemosensor, being emissive at 390 nm at acidic pH and non-emissive at basic pH. The chemosensor is able to detect Zn²⁺ and Cd²⁺ in an aqueous medium (acetonitrile–water, 4:1 v/v) at neutral pH through a CHEF effect upon metal ion coordination. Paramagnetic metal ions (Cu²⁺) and heavy atoms (Pb²⁺, Hg²⁺) resulted in a quenching of fluorescence or very low emission. Conclusions: The new cyclophane macrocycle L was revealed to be a selective PET-regulated chemosensor for Zn²⁺ and Cd²⁺ in an aqueous medium, being able to bind up to two and one metal cations, respectively. The molecule showed a shifted emission towards the visible region compared to similar systems, suggesting a co-planar conformation of the aromatic fragment upon metal coordination. All these data are supported by both experimental measurements and theoretical calculations.

Molecular aggregation and the hydrophobic effect explain the solvatomorphism and sorption behavior of a cyclic hexapeptoid.

A new series of ligands containing the 2‐(2‐hydroxy‐3‐ naphthyl)‐4‐methylbenzoxazole (HNBO) fluorophore showed selectivity for Mg²⁺ ions, without the interference of Ca²⁺. The most promising representative L3 resulted the best performing sensor for Mg²⁺ both in solution and embedded in an all‐solid‐state optode, especially towards real samples of drinkable water.

Bis-squaramide receptors L1–L4 bearing a dansyl moiety were considered as fluorescent probes for non steroidal antinflamatory drugs naproxene and ketoprofen.

We describe the energetic landscape beyond the solid-state dynamic behavior of a cyclic hexapeptoid decorated with four propargyl and two methoxyethyl side chains, namely, cyclo-(Nme-Npa₂)₂, Nme = N-(methoxyethyl)glycine, Npa = N-(propargyl)glycine. By increasing the temperature above 40 °C, the acetonitrile solvate form 1A starts to release acetonitrile molecules and undergoes a reversible single crystal-to-single crystal transformation into crystal form 1B with a remarkable conformational change in the macrocycle: two propargyl side chains move by 113° to form an unprecedented “CH-π zipper”. Then, upon acetonitrile adsorption, the “CH-π zipper” opens and the crystal form 1B transforms back to 1A. By conformational energy and lattice energy calculations, we demonstrate that the dramatic side-chain movement is a peculiar feature of the solid-state assembly and is determined by a backbone conformational change that leads to stabilizing CH···OC backbone-to-backbone interactions tightening the framework upon acetonitrile release. Weak interactions as CH···OC and CH-π bonds with the guest molecules are able to reverse the transformation, providing the energy contribution to unzip the framework. We believe that the underlined mechanism could be used as a model system to understand how external stimuli (as temperature, humidity, or volatile compounds) could determine conformational changes in the solid state.