A new series of alkoxy- and polypyridine-bridged rhenium molecular rectangles of formulae {[Re(CO)3(OC₅H₁₁)]4(L)₂}, with OC₅H₁₁ = 1-pentoxy, L = PCA (4-pyridinecarboxaldehyde azine) and 4,4 ‘-azpy (4,4 ‘-azobis(pyridine)), were synthesized and characterized by spectroscopic and diffraction techniques. Quenching of fluorescence of aromatic hydrocarbons by these complexes was studied by stationary and dynamic techniques. The quenching mechanism proved to be predominantly static and the Stern-Volmer constants indicated a decrease of the extent of C-H center dot center dot center dot pi interactions with decreasing length of the linkers that form the molecular rectangles.