The majority of the melts formed were found to recrystallize partially upon cooling from temperatures (near their Tm-offset). To form the glasses, annealing near their Td was necessary, which suggests a small degree of decomposition of the organic linker occurs. Those structures possessing bulkier TPnA A-site cations remained viscous after quenching at room temperature, and solidified only after several days. The viscous character of ag [TPnA][Fe(dca)3] and ag [TPnA][Co(dca)3] is linked to their high ΔSf values upon melting and below-room temperature Tgs. Alongside relatively low values of Tg below room temperature indicates the kinematic similarity of this dca based ABX3 melts with dca based ionic liquids. Such basic observations may provide further rules for the design of glass forming hybrid structures.