A push-pull macrocycle with both linearly conjugated and cross-conjugated bridges.

A series of shape-persistent macrocycles featuring both m-phenylene and 2,5-thiophene linkers has been synthesized, including an example where they bridge electron-rich (veratrole) and electron-poor (phthalimide) units. Charge transfer in this "push-pull macrocycle" has been investigated by UV-vis and fluorescence spectroscopies and DFT calculations. The effect of pairing structurally distinct conjugated bridges is discussed in the context of acyclic and symmetrical macrocyclic analogs.

Push-pull macrocycles: donor-acceptor compounds with paired linearly conjugated or cross-conjugated pathways.

Two-dimensional π-systems are of current interest in the design of functional organic molecules, exhibiting unique behavior for applications in organic electronics, single-molecule devices, and sensing. Here we describe the synthesis and characterization of "push-pull macrocycles": electron-rich and electron-poor moieties linked by a pair of (matched) conjugated bridges. We have developed a two-component macrocyclization strategy that allows these structures to be synthesized with efficiencies comparable to acyclic donor-bridge-acceptor systems.