The reaction of [Cu(MeCN) 4 ]BF 4 with o-, m-, or p-dicyanobenzene (DCB) or o-, m-, or p-cyanopyridine (CPy) in the presence of two equivalents of PPh 3 produces DCB-or CPybridged copper(I) complexes. Cyclic dimers are formed for the ortho ligands, and zigzag polymers are formed using the para ligands. m-DCB produces a polymer, however m-CPy results in a cyclic trimer. Multiple lattice-bound solvates are formed upon crystallization of the o-DCB dimer from various solvents. A total of 11 X-ray crystal structures are reported for [Cu n (PPh 3) 2n (bridge) n ](BF 4) n •(solvent): bridge = o-DCB, n = 2, solvent (per dimer) = none, ½ CH 2 Cl 2 , CH 2 Cl 2 , 2 CHCl 3 /H 2 O, or 2 THF; bridge = m-DCB, n = ∞, solvent = none; bridge = p-DCB, n = ∞, solvent = CH 2 Cl 2 (two polymorphs), bridge = o-CPy, n = 2, solvent (per dimer) = 2 toluene; bridge = m-CPy, n = 3, solvent = none; bridge = p-CPy, n = ∞, solvent = ½ acetone. All complexes are photoluminescent with excitation in the range 340-400 nm. The meta complexes emit in the blue region, while the other complexes emit in the green. Dimer complexes of o-DCB exhibit structural flexibility in the central macrocyclic ring. Complexes of m-DCB and p-CPy show orientational disorder in the ligand. Polymeric complexes show helicity. Smaller Stokes

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