There are only six previous reports of single crystal structures of PDI-containing MOFs, with three of those employing ligands based on a 1,2,6,7-tetrachloroperylene-3,4,9,10-tetracarboxylic acid diimide core. Although the other reported examples use ligands with unsubstituted perylene cores, the use of the tetrachloro-PDI, which has a twisted perylene core, suggests a primary reason that PDI-MOFs are less studied than their NDI analogues. PDIs exhibit notoriously challenging solubility, primarily due to inter-PDI p-p stacking interactions, and, in combination with solvents commonly used for MOF synthesis such as N,N'-dimethylformamide (DMF), the growth of PDI-MOF single crystals, or even crystalline material can be a formidable challenge. In this study we demonstrate that functionalisation of the imide substituent of the PDI group allows enhanced solubility facilitating growth of crystalline MOF materials. Further, we demonstrate for the first time, the growth of PDI-based MOFs on transparent electrode surfaces that allow (spectro)electrochemical characterisation of the PDI-based MOFs, affording unequivocal interpretation of the phenomena underpinning electrochromic behaviour.