A major challenge for molecular magnetism has been the weakness of the magnetic interactions between paramagnetic ions, especially compared to the pure elements and simple oxides, where strong exchange can be produced through direct overlap of the magnetic orbitals, or a single intervening anion. Developing our understanding of how crystal chemistry determines magnetic interactions will aid us realising both in producing practical magnetism, and, critically, in targeting exotic magnetic phases requiring careful balance of interactions. The cyanide Prussian Blue analogues provide an outstanding example of how crystal engineering can be used to optimise magnetic properties, with the enhancement of magnetic Curie temperatures T C from 5.6(1) K for Prussian Blue itself, Fe 4 [Fe(CN) 6 ] 3 • xH 2 O, up to 376 K, KV[Cr(CN) 6 ]. Thiocyanate as a pseudohalide ligands is well-known for its optical properties, but control over its magnetism is much less developed, with most focus either on either the two dimensional pseudobinaries or frameworks incorporating additional organic coligands . Recently, some of us showed that the magnetism of the layered pseudobinary M(NCS) 2 , M = Cu, Ni, Co, Fe and Mn, can be qualitatively explained on the basis of changing orbital occupation and size, leading to enhancement of interactions and uncovering layered antiferromagnetism. Three dimensionally connected, perovskite analogue structured materials would be of particular interest as magnets, but thus far no frameworks containing only paramagnetic metals on the Msite has been synthesised, as the sulfur terminus requires a softer metal such as Cd 2+ , Bi 3+ , or Pt 4+ , leading to the "double perovskite" structure. These sulfur-bonding metals are all diamagnetic, which suggests that the paramagnetic ions in thiocyanate Prussian Blue analogues would be magnetically isolated. However, were these paramagnetic metal ions to be magnetically connected through superexchange pathways, these frameworks would be examples of magnets with the J 1 -J 2 face-centered cubic model [Fig. ], which is both the source of exotic frustrated states, and common to both rock-salt structured oxides and double perovskites .