GROUND-STATE AND EXCITED-STATE PROPERTIES OF RUTHENIUM(II) COMPLEXES CONTAINING TRIDENTATE AZINE LIGANDS, RU(TPY)(BPY)L(2+), WHERE L IS A POLYMERIZABLE ACETYLENE

A series of polypyridyl ruthenium(II) complexes containing monodentate pyridyl- and cyano-substituted acetylenes have been prepared. Complexes of the type Ru(tpy)(bpy)L(2+) (where tpy = 2,2':6':2''-terpyridine (C15H11N3), bpy = 2,2'-bipyridine (C10H8N2), and L = pyridine (py) (C5H5N), pyridylacetylene (PA) (C7H5N), phenylpyridylacetylene (PPA) (C13H9N), dipyridylacetylene (DPA) (C12H8N2). CH3CN, cyanoacetylene (C.4) (C3HN), and cyanophenylacetylene (CPA) (C9H5N)) have been prepared, and their synthesis and characterization are reported herein. The complexes [Ru(tpy)(bpy)(PPA)](PF6)(2).(CH3)(2)CO, [RU(tpy)(bpy)(PA)](PF6)(2).(CH3)(2)CO, and [Ru(tpy)(bpy)(CH3CN)](PF6)(2) have been crystallized and the crystal structures determined. [Ru(tpy)(bpy)(CH3CN)](PF6)(2) crystallizes in the monoclinic P2(1)/c space group with a 19.419(5) Angstrom, b = 10.702(4) Angstrom, c = 16.380(5) Angstrom, beta = 112.09(2)degrees, Z = 4, R = 0.0725, and R(w) = 0.0933. [Ru(tpy)(bpy)(PA)](PF6)(2).(CH3)(2)CO crystallizes in the triclinic P ($) over bar 1 space group with a = 9.936(2) Angstrom, b = 10.261(2) Angstrom, c = 19.270(3) Angstrom, alpha = 77.65(1)degrees, beta = 85.19(1)degrees, gamma = 84.69(1)degrees, Z = 2, R = 0.0427, and R(w) = 0.0492. [Ru(tpy)(bpy)(PPA)](PF6)(2).(CH3)(2)CO crystallizes in the triclinic P ($) over bar 1 space group with a = 10.235(3) Angstrom, b = 13.094(1) Angstrom, c = 16.593(2) Angstrom, alpha = 79.55(1)degrees, beta = 80.76(2)degrees, gamma = 89.01(2)degrees, Z = 2, R = 0.0456, and R(w) = 0.0602. The inclusion of the functionalized acetylene groups makes these complexes possible precursors to metal-coordinated polyacetylenes.