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We herein describe a new design principle to achieve B/N‐doped cyclophane where an electron‐donor block of three triarylamines (Ar₃N) and an acceptor block of three triarylboranes (Ar₃B) are spatially separated on opposite sides of the π‐extended ring system. DFT computations revealed the distinct electronic structure of theblock‐type macrocycleMC‐b‐B3N3with a greatly enhanced dipole moment and reduced HOMO–LUMO energy gap in comparison to its analogue with alternating B and N sites,MC‐alt‐B3N3. The unique arrangement of borane acceptor Ar₃B and amine donor Ar₃N components inMC‐b‐B3N3induces exceptionally strong intramolecular charge transfer in the excited state, which is reflected in a largely red‐shifted luminescence at 612 nm in solution. The respective linear open‐chain oligomerL‐b‐B3N3was also synthesized for comparison. Our new approach to donor–acceptor macrocycles offers important fundamental insights and opens up a new avenue to unique optoelectronic materials.

We herein describe a new design principle to achieve B/N‐doped cyclophane where an electron‐donor block of three triarylamines (Ar₃N) and an acceptor block of three triarylboranes (Ar₃B) are spatially separated on opposite sides of the π‐extended ring system. DFT computations revealed the distinct electronic structure of theblock‐type macrocycleMC‐b‐B3N3with a greatly enhanced dipole moment and reduced HOMO–LUMO energy gap in comparison to its analogue with alternating B and N sites,MC‐alt‐B3N3. The unique arrangement of borane acceptor Ar₃B and amine donor Ar₃N components inMC‐b‐B3N3induces exceptionally strong intramolecular charge transfer in the excited state, which is reflected in a largely red‐shifted luminescence at 612 nm in solution. The respective linear open‐chain oligomerL‐b‐B3N3was also synthesized for comparison. Our new approach to donor–acceptor macrocycles offers important fundamental insights and opens up a new avenue to unique optoelectronic materials.