Journal of Physical Chemistry B, Vol.109, No.40, 18935-18941, 2005
Orientation tuning of a polypyridyl Ru(II) complex immobilized on a clay surface toward chiral discrimination
The present work reports an attempt to elucidate a stereoselective energy-transfer system by immobilizing a chiral metal complex on a clay surface. The metal complex used was [Ru(bpY)(2)L-i](2+) with L, = bpy (2,2'-bipyridine), L-2 = 4,4'-diundecyl-2,2'-bipyridine, and L-3 = 5,5'-diundecyl-2,2'-bipyridine. The adsorption structure of [Ru(bpy)(2)Li](2+) was studied by means of electric dichroism measurements on an aqueous dispersion of a colloidal clay. It was found that the molecular orientation of the adsorbed Ru(II) complex was affected remarkably by the positions of the alkyl chains on the bpy ligand; that is, the angle of the 3-fold or pseudo-3-fold symmetry axis of the Ru(II) complex with respect to the surface normal was obtained to be 24 degrees, 30 degrees, and 52 degrees for i = 1, 2, and 3, respectively. The efficiency of the energy-transfer was determined by photoluminescence quenching measurements between the adsorbed Ru(II) complex and [Ru(acac)(3)] (acac = acetylacetonate) in solution. As a result, stereo selectivity appeared most for the case of [Ru(bpy)(2)L-3](2+) in which its two helically twisted bpy ligands were projected in an outward direction.