A series of H-bonded supramolecular architectures were built from monofunctional M-C = C-R and bifunctional R-C = C-M-C = C-R trans-alkynylbis(1,2-bis(diphenylphosphino)ethane)ruthenium(II) complexes and pi-conjugated modules containing 2,5-dialkoxy-p-phenylene. incorporation on each partner of a cyanuric end and of the complementary Hamilton receptor provided the necessary means to keep the constituents together via strong hydrogen bonding. Characterization of all architectures has been performed on the basis of NMR and photophysical methods. In particular, the formation of a Hamilton receptor/cyanuric acid complex has been exemplified by an X-ray single-crystal structure determination. Both self-assembly and accurate modification of the complementary blocks were ensured in such a way that the resulting materials maintain the responsiveness of the electron-rich 2,5-dialkoxy-p-phenylene spacers toward nitroaromatics.