A concise, highly regioselective synthesis of 1, 8-dibromo-4, 5-dialkoxypyrenes has been developed and exploited in the synthesis of some 1, 8-pyrenylene− ethynylene macrocycles. The 1H NMR data and NICS calculations indicate that there is little or no macrocyclic ring current. Concentration-dependent UV− visible studies indicate no aggregation at low concentration, but 8b forms dimers with voids suitable for intercalation of small molecules ...