A series of coordination polymer materials incorporating the highly anisotropic 2-(2-pyridyl)-1,10-phenanthroline (phenpy) building block have been synthesized and structurally characterized. M(phenpy)[Au(CN)(2)](2) (M = Cd; Mn) are isostructural and form a 1-D chain through bridging [Au(CN)(2)](-) units and extend into a 2-D sheet through aurophilic interactions. M(phenpy)(H2O)[Au(CN)(2)](2)center dot 2H(2)O (M = Cd, Mn, and Zn) are also isostructural but differ from the first set via the inclusion of a Water molecule into the coordination sphere, resulting in a 1-D topology through aurophilic interactions. In(phenpy)(Cl)(2)[Au(CN)(2)]center dot 0.5H(2)O forms a dimer through bridging chlorides and contains a free [Au(CN)(2)](-) unit. In the plane of the primary Crystal growth direction, the birefringence values (Delta n) of 0.37(2) (Cd(phenpy)[Au(CN)(2)](2)), 0.50(3) (In(phenpy)(Cl)(2)[Au(CN)(2)]center dot 0.5H(2)O), 0.56(3) and 0.59(6) (M(phenpy)(H2O)[Au(CN)(2)](2)center dot 2H(2)O M = Cd and Zn, respectively) were determined. beta, a structural parameter defined by phenpy units rotated in the A-C plane relative to the light propagation (C) direction, was found to correlate to Delta n magnitudes. The addition of a carbon-carbon double bond to terpy has increased the molecular polarizability anisotropy of the building block, and all structures have reduced deviation from planarity in comparison to terpy and terpy derivative structures, leading to these higher Delta n values, which are among the highest reported for crystalline solids.