Shape-Persistent π-Conjugated Macrocycles with Aggregation-Induced Emission Property: Synthesis, Mechanofluorochromism, and Mercury(II) Detection.

Abstract

Shape-persistent conjugated macrocycles are fundamentally important because of their unique structure and properties. Herein, a series of π-conjugated macrocycles with a shape-persistent architecture, an adaptive backbone, and aggregation-induced emission (AIE) properties are synthesized via oxidative coupling of acetylene-terminated tetraphenylethylene precursor with a half-ring topology and following transformation from butadiynylene linkers into thienylene ones. Characterization by NMR spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry provided unambiguous proofs for the macrocyclic structures. In particular, the free rotation of aromatic rings in the rigid macrocyclic backbone was validated by two-dimensional NMR spectroscopy, variable-temperature NMR measurements, and theoretical calculations. Moreover, these shape-persistent macrocyclic chromophores all exhibited obvious AIE phenomena and remarkable mechanofluorochromism behaviors with a red-shifted luminescence upon grinding and blue-shifted emission after solvent annealing. Also, the introduction of S atoms into the macrocyclic frameworks endowed the macrocyclic luminogen the capability to selectively detect mecury(II) ions in aqueous media among other metal ions.