Synthesis, emission, and molecular orbital studies of luminescent hafnium thiolate complexes. Crystal structures of (eta(5)-C5Me5)(2)Hf(SR)(2) (R = Bu-n, C6H5, C6H4OMe-p)

A series of luminescent hafnium thiolate complexes (eta(5)-C5Me5)(2)Hf(SR)( 2) (R = Bu-n, C6H5, C6H4OMe-p, C(6)H(4)tBu-p) have been synthesized by the reaction of (eta(5)-C5Me5)(2)HfCl2 with LiSR and shown to exhibit rich lumi nescence behavior. The crystal structures of (eta(5)-C5Me5)(2)Hf((SBu)-Bu-n )(2), (eta(5)-C5Me5)(2)Hf(SC6H5)(2), and (eta(5)-C5Me5)(2)Hf(SC6H4OMe-p)(2) have been determined. Fenske-Hall molecular orbital calculations on the ha fnium thiolate complexes reveal a thiolate-based HOMO and a LUMO that is ma inly composed of hafnium d character.