Convenient, zirconocene-coupling routes to germole- and thiophene-containing macrocycles with triangular geometries

Reactions of zirconacyclopentadiene-coupled macrocycles with S2Cl2 or GeCl4 gave new macrocycles containing thiophene and dichlorogermole groups, respectively. The germoles, synthesized in high yields, possess labile chloride substituents that are readily displaced via nucleophilic substitution reactions. These germole-containing macrocycles are potentially useful as supramolecular building blocks. A macrocyclic trithiophene compound, with 1,4-phenylene groups that bridge the thiophene rings, was characterized by X-ray crystallography. The X-ray structure of a related trigermole macrocycle, with bridging biphenylene groups, is also presented.