Three new compounds, {U-2(H2O)(10)(O)[Pt(CN)(4)](3)}center dot 4H(2)O, {Th-2(H2O)(10)(OH)(2)[Pd(CN)(4)](3)}center dot 8H(2)O, and {(UO2)(2)(DMSO)(4)(OH)(2)[Ni(CN)(4)]}, hi the actinide tetracyanometallate, An(x)[M(CN)(4)](y), class of compounds have been synthesized and characterized by confocal Raman spectroscopy and single crystal X-ray diffraction. These compounds contain unique structures illustrating dimeric actinide species. The absence of intense charge transfer emission in the visible range for {U-2(H2O)(10)(O)[Pt(CN)(4)](3)}center dot 4H(2)O, as compared to the platinum starting material, is unusual because of the presence of pseudo-one-dimensional Pt center dot center dot center dot Pt chains in this compound. Confocal Raman spectroscopy of the cyanide stretching region provides insight into the binding domain (mono-, bi-, tri-, tetradentate) of the tetracyanometallates in these novel structures