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. Complex es 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) (C5 H5N), pyridylacetylene (PA) (C7H5N), phenylpyridylacetylene (PPA) (C13 H9N), dipyridylacetylene (DPA) (C12H8N2). CH3CN, cyanoacetylene (C.4) (C3HN), and cyanophenylacetylene (CPA) (C9H5N)) have been prepared, an d their synthesis and characterization are reported herein. The comple xes [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) c rystallizes in the monoclinic P2(1)/c space group with a 19.419(5) Ang strom, 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 ($) over bar 1 space g roup with a = 9.936(2) Angstrom, b = 10.261(2) Angstrom, c = 19.270(3) Angstrom, alpha = 77.65(1)degrees, beta = 85.19(1)degrees, gamma = 84 .69(1)degrees, Z = 2, R = 0.0427, and R(w) = 0.0492. [Ru(tpy)(bpy)(PPA )](PF6)(2).(CH3)(2)CO crystallizes in the triclinic P ($) over bar 1 s pace 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, gam ma = 89.01(2)degrees, Z = 2, R = 0.0456, and R(w) = 0.0602. The inclus ion of the functionalized acetylene groups makes these complexes possi ble precursors to metal-coordinated polyacetylenes.