A series of luminescent polyalkynyl rhenium(I) compounds that contain fac-tricarbonyl ligands and 4,4^'-t-butyl-2,2^'-bipyridine metal chelating units have been synthesized using the Eglinton coupling reaction.  These molecules contain varying numbers of -(acetylene)_n- (n = 4-6) units as the bridging ligand and can serve as models for understanding electron and charge transfer through pseudo-one-dimensional sp carbon chains.  The spectroscopic properties of these new molecular wires have been fully examined.  The steady-state emission spectra and luminescent lifetimes in solid poly(methyl methacrylate) (PMMA) matrices at 77 K and in THF solutions at room temperature have been recorded.  These luminescent data revealed the coexistence of conformational isomers with the two bipyridine planes either cis- or trans- relative to each other.  The time-resolved infrared spectroscopy and the quantum chemical modeling have revealed that the charge transfer properties of these compounds are highly dependent upon the length of the sp carbon chain.  As the number of bridging acetylene ligands increases from 4 to 6, the emitting excited state also varies dramatically.  Quantum chemical modeling and spectroscopic evidences have revealed that compound Re(CC)₄Re emits from two states: a state composed of an admixture of  a dominant amount of ³LLCT (p_C≡C → p^*_bpy) and a tiny amount of ³MLCT (dp_Re → p^*_bpy), and a  ligand centered ³pp^*_C≡C state.  The orbital nature of the lowest emitting triplet manifold for compound Re(CC)₅Re originates from a single state that is an admixture of a dominant amount of ³LLCT (p_C≡C → p^*_bpy) and a tiny amount of ³MLCT (dp_Re → p^*_bpy).  Compound Re(CC)₆Re also phosphoresces  from a single excited state with an orbital nature similar to that observed for compound Re(CC)₅Re, but with a great number of excited states lying close in energy.