Strong Chiroptical Effects in the Absorption and Emission of Macrocycles Based on the 2,5-Diaminoterephthalate Minimal Fluorophore

Chiral fluorescent macrocycles consisting of two to four units of dimethyl 2,5-diaminoterephthalate can be readily synthesized in a one-pot manner from inexpensive building blocks. Depending on the concentration, either a paracyclophane-like dimer with closely stacked benzene rings or a triangular trimer is the main product of the reaction. The macrocycles exhibit fluorescence in solution as well as in the solid state with maxima that are red-shifted with decreasing size of the macrocyclic ring and are observed at wavelengths from 590 (tetramer in solution) to 700 nm (dimer in the solid state). Chirality dictates the differential absorption and emission of circularly polarized light by these molecules. The ECD and CPL effects are particularly strong for the trimer, which is characterized by relatively large dissymmetry factors g(abs)=& PLUSMN;2.8x10(-3) at 531 nm and g(lum)=& PLUSMN;2.3x10(-3) at 580 nm in n-hexane, being at the same time highly luminescent (& phi;(fl)=13.7 %). Despite the small chromophore, the circularly polarized brightness B-CPL of 2.3 dm(3) mol(-1) cm(-1) is comparable to values reported for other classes of established CPL emitters in the visible region, such as expanded helicenes or larger & pi;-conjugated systems.