A Synthetic Approach Towards Interlocked π-Conjugated Macrocycles

A method for the synthesis of interlocked π‐conjugated macrocycles is described. Starting from 2,9‐bis(oligothienyl)[1,10]phenanthrolines, (trimethylsilyl)acetylene groups were introduced at the terminal thiophene rings by selective iodination and subsequent Sonogashira–Hagihara coupling. Subsequently, we applied our recently developed metal‐template approach to macrocyclization reactions by treating the deprotected acetylenes with cis‐[Pt(dppp)Cl2] to yield a platina‐macrocycle. Based on this synthetic knowledge, by a multiple transition‐metal‐template protocol we accomplished the synthesis of a copper(I)–catenate consisting of two interlocked π‐conjugated macrocycles which contain oligothiophene, diacetylene and phenanthroline units. Conclusive evidence for the new structures came from a detailed characterization of the platina‐macrocycles and catenates by ESI‐FT‐ICR and tandem mass spectrometry experiments. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)