Highly Crowded Twisted Thienylene-Phenylene Structures: Evidence for Through-Space Orbital Coupling in a [4]Catenated Topology.

Sterically highly crowded and twisted thienylene-phenylenes are synthesized and structurally characterized. Single-crystal X-ray structure analyses and theoretical studies give evidence of through-space delocalization of π-electrons of peripheral (hetero)aromatic rings in toroidal and catenated topology.