On the role of PES data in the identification of metal-metal charge transfer bands in clusters of clusters

Abstract

The clusters of M2[O2CCCo3(CO)9]4-n[O2CR]n, where M is Cr, n= O; where M is Mo, n = 0,1, R is CH3; where M is W, n=0; exhibit allowed transitions with absorvance maxima that correlate with the lowest ionization energy of M2(O2CMe)4. An analysis of this correlation, in conjunction with molecular orbital models of electronic structure, allows these adsorptions to be assigned to charge transfer transitions between the group 16 dimetal center and the tricobalt cluster substituent on the carboxylate ligand functionality. The characteristics of this metal-metal charge transfer transition should be amenable to further control by variation in substituent cluster properties.