Following a route described by Müllen et al. we improved the preparation of 1,2,3-tris(3″-iodobiphenyl-2′-yl)benzene (4). During the required iododesilylation with iodine monochloride the unexpected formation of a mono-chlorinated compound 6 as major product was observed, when an excess of the iodination reagent was employed. The reaction mechanism for the formation of this compound involving an oxidizing process is discussed. X-ray crystallography of the subsequent alkynylated product 7 proves the location of the chlorine atom at the central benzene ring. The related compound 5 was likewise investigated by X-ray analysis revealing a preferred solid-state conformation (“2-up-1-down”) different from that of the chlorinated compound (“propeller” conformation). Compound 7 showed remarkable conformational dynamics in solution as observed by 1H NMR spectroscopy. Temperature-dependent measurements allowed the calculation of an energy difference of two major conformers of ca. 2 kJ/mol and a rotational barrier ΔGrot of ca. 77 kJ/mol. These values were convincingly confirmed by DFT calculations. A subsequent Sonogashira reaction of 4 with a suitable bipyridine derivative provided a unique trivalent bipyridine derivative.