Methylation of S1 and S2 by reaction with excess MeI in DMF at 90 ºC gave the desired carbonylpyridinium products (1 and 2) as pale-yellow solids with quantitate yields. Conveniently, due to the high reaction efficiency, no tedious column chromatography is needed to isolate the intermediates and final products in pure form. All the intermediates and final products were fully characterized by 1 H and C NMR spectroscopy, as well as high-resolution mass spectrometry (HRMS) (see SI). The structures of 1 and S2 were further confirmed by single-crystal X-ray crystallography (Figure and). Common features are a highly planar central biphenylene or bithienylene bridge, while the carbonylpyridine (or pyridinium) units are twisted out of the central plane. The crystal data and structural refinement parameters are summarized in Table . To further extend the basic conjugated framework, a dibrominated compound 3 was designed that allows for subsequent cross-coupling reactions. The two-step synthesis of 3 is similar to that of 2.