Coordination polymers (CPs) with reversible phase changes between amorphous and crystalline states have recently become of interest for potential Phase-Change Memory applications. Efficient CPs have to exist in amorphous and crystalline phases with remarkably different optical, conductive or electrical properties which can be reversed by the application of an external stimuli to get the set/reset outputs (Fig. 1). Thus their physical properties are strongly affected by the presence or absence of long range order, defects or different connectivities. While the structures of the crystalline forms have been well characterized by traditional crystallographic approaches relying on the periodicity of the lattice, the atomic connectivity of CPs in the amorphous state is not yet understood. Thus, we propose to perform a total scattering experiment of the two promising CPs, [Au(SPh)]n and [M(1,2,