Making connections between molecular framework and atomic inorganic materials can be very productive, both better to understand the structures of molecular framework materials and also to suggest potential structure-types that have not yet been realized in functional materials. Notably, none of the missing binary thiocyanates are present in the extremely large hypothetical materials datasets recently produced. This perhaps arises from the difficulty current computational approaches have with molecule-containing materials, which are typically metastable thermodynamically despite their synthetic accessibility. This review also highlights that the experimental literature continues to offer opportunities to discover new functions through reinvestigation of known materials. For example there are nine binary and ternary thiocyanates which are structurally two-dimensional with neutral layers but that have not been investigated as potential monolayer materials (M(NCS) 2 , M = Cu, Ni, Co, Fe, Mn, Zn, Hg; ZnPb(NCS) 4 and Mn 2 Hg(NCS) 6 ) and more than half of these have not been previously proposed to be stable as monolayers theoretically. This suggests that the chemical insight and deep searching of chemical literature can still be a fruitful route for uncovering brand new materials and useful functionality. In particular, although the majority of materials described in this review were described using salt-metathesis, alternative synthetic routes, whether classical or using more modern techniques, could allow for the realization of presently unknown compounds.