Synthesis, Structural, And Photoluminescence Studies Of Gd(Terpy)(H2o)(No3)(2)M(Cn)(2) (M = Au, Ag) Complexes: Multiple Emissions From Intra- And Intermolecular Excimers And Exciplexes

The highly luminescent bimetallic cyanide materials, Gd(terpy)(H2O)(NO3)(2)M(CN)(2) (M = Au, Ag; GdAu and GdAg, respectively) are quick and easy to synthesize under ambient conditions. A characteristic feature exhibited by both solid-state compounds is an intense red emission when excited with UV light. Additionally, GdAu exhibits a broad-band green emission upon excitation in the near UV region. A combination of structural and spectroscopic results for the compounds helps explain the underlying conditions responsible for their unique properties. Single-crystal X-ray diffraction experiments expose their structural features, including the fact that they are isostructural. Crystallographic data for the representative GdAu compound (Mo K-w lambda = 0.71073 angstrom, T = 290 K): triclinic, space group P (1) over bar, a = 7.5707(3) angstrom, b = 10.0671(4) angstrom, c = 15.1260(4) angstrom, alpha = 74.923(3)degrees, beta = 78.151(3)degrees, gamma = 88.401(3)degrees, V = 1089.04(7) angstrom(3), and Z = 2. Although the compounds crystallize as dimers containing M.-M distances smaller than the sum of their van der Waals radii, the Au center dot center dot center dot Au (3.5054(4) angstrom) and/or the Ag center dot center dot center dot Ag (3.6553(5) angstrom) interactions are relatively weak and are not responsible for the low energy red emission. Rather, the green emission in GdAu presumably originates from the [Au(CN)(2)(-)](2) dimeric excimer, while the [Ag(CN)(2)(-)](2) dimers in GdAg do not display visible emission at either 290 or 77 K. The unusual red emission exhibited by both compounds likely originates from the formation of an excited state exciplex that involves intermolecular pi-stacking of 2,2':6',2 ''-terpyridine ligands. The room-temperature and low-temperature steady-state photoluminescent properties, along with detailed time-dependent, lifetime, and quantum yield spectroscopic data provide evidence regarding the sources of the multiple visible emissions exhibited by these complexes.