Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru 2(μ-η 4-C 2O 4)(MeOH) 2(η 6-pcymene) 2](O 3SCF 3) 2 (1a) or [Ru 2(μ-η 4-N,N'-diphenyloxamidato)(MeOH) 2(η 6-p-cymene) 2](O 3SCF 3) 2 (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4- benzoquinonato (dhbq) bridged binuclear complex [Ru 2(μ- η 4-C 6H 2O 4)(MeOH) 2(η 6-p-cymene) 2](O 3SCF 3) 2 (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the selfassembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear ( 1H, 13C and 19F) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 Å × 12.39 Å. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis. © 2012 Shanmugaraju et al.