Expanding the [2.2]Paracyclophane Framework: A New Synthetic Entry to π ‐Extended Derivatives

We a complementary synthetic approach to π-expanded [2.2]paracyclophanes based on aryne annulation chemistry. The method provides access to anti-anthracenophane and new tetracenophane derivatives from a common cyclophane precursor. The resulting compounds were examined by single-crystal X-ray diffraction, optical spectroscopy, and quantum-chemical calculations. The structural studies reveal that the rigid [2.2]paracyclophane framework strongly influences molecular organization in the solid state, while the spectroscopic data demonstrate substantial electronic communication between the cofacially arranged acene units. The calculations support the experimental observations and provide insight into the electronic structure and aromaticity of these π-expanded systems. This work broadens the synthetic chemistry of acenophanes and highlights their potential as shape-defined building blocks for functional organic materials.