Stereomutation and chiroptical bias in the kinetically controlled supramolecular polymerization of cyano-luminogens

Abstract

The synthesis of two pairs of enantiomeric cyano-luminogens 1 and 2, in which the central chromophore is a p-phenylene or a 2,5-dithienylbenzene moiety, respectively, is described and their supramolecular polymerization under kinetic and thermodynamic control investigated. Compounds 1 and 2 form supramolecular polymers by quadruple H-bonding arrays between the amide groups and the π-stacking of the central aromatic moieties. In addition, the peripheral benzamide units are able to form intramolecularly H-bonded pseudocycles that behave as metastable monomer M* thus affording kinetically and thermodynamically controlled aggregated species AggI and AggII. The chiroptical and emissive features of compounds 1 and 2 strongly depend on the aggregation state and the nature of the central aromatic unit. Compounds 1 exhibit a bisignated dichroic response of different intensity but with similar sign for both AggI1 and AggII1 species, which suggests the formation of helical aggregates. In fact, these helical supramolecular polymers can be visualized by AFM imaging. Furthermore, both AggI and AggII species formed by the self-assembly of compounds 1 show CPL (circularly polarized light) activity of opposite sign depending on the aggregation state. Thienyl-derivatives 2 display dissimilar chiroptical, morphological and emissive characteristics for the corresponding kinetically and thermodynamically controlled aggregated species AggI and AggII in comparison to those registered for compounds 1. Thus, a stereomutation phenomenon is observed in the AggI2 → AggII2 conversion. In addition, AggI2 is arranged into nanoparticles that evolve to helical aggregates to afford AggII2. The dissimilar chiroptical and morphological features of AggI2 and AggII2 are also appreciated in the emissive properties. Thus, whilst AggI2 experiences a clear AIE (aggregation induced emission) process and CPL activity, the thermodynamically controlled AggII2 undergoes an ACQ (aggregation caused quenching) process in which the CPL activity is cancelled.