Communication pubs.acs.org/IC
Phosphorescent Decanuclear Bimetallic Pt6M4 (M = Zn, Fe) Tetrahedral Cages Yuzhen Zhang, Matthew R. Crawley, Cory E. Hauke, Alan E. Friedman, and Timothy R. Cook* Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260, United States S Supporting Information *
two terminal bipyridyl groups.34 As part of their studies, the changes in the photophysical properties upon titration of this ligand with ZnII were discussed. In their experiments, ZnII was added until no further spectral changes were observed, attributed to the formation of a coordination polymer. We anticipated that if ZnII or other metal ions capable of tris-chelating coordination environments were added in proper stoichiometries, the directionality of these building blocks would enable the formation of tetrahedral cages similar to those pioneered by Raymond and recently studied by Nitschke and others.35−37 Examples of such architectures employ organic bis-chelating ligands rather than organometallic donors. Moreover, there is no phosphorescent emission reported for those cages.38−40 Herein, we report two nanoscale, discrete phosphorescent cages, [ZnII4L6](PF6)8 (C1) and [FeII4L6](OTf)8 (C2), that selfassemble when Zn(NO3)2·6H2O or Fe(OTf)2 is mixed with the linker Pt(PE3)2(CC-bpy)2 (L) in a 2:3 ratio. C1 exhibited phosphorescence emission centered at 545 nm with a quantum yield of 10% in N2-degassed acetonitrile at 25 °C, and C2 exhibited phosphorescence centered at 517 nm with a quantum yield of
