Covalent functionalization of 1,4-benzenedicarboxylate (bdc) with methoxyethoxy groups induces conformational freedom in this molecule. Applying these 2,5-disubstituted bdc derivatives in metal-organic framework synthesis together with 4,4'-bipyridine as coligand yields novel honeycomb-like structures. The cylindrical channels of these materials are populated with flexible groups, which act as molecular gates for guest molecules. This allows highly selective sorption of CO(2) over N(2) and CH(4).