The porous coordination polymers (PCPs) of general formula {Fe(bpac)[M(CN)₄]}·guest (M = Pt, Pd) exhibit larger channels than previously synthesised 3D-Hofmann-like PCP. The channels are partially occupied by uncoordinated guest bpac ligands and labile H₂O molecules. These PCPs exhibit very scarce cooperative spin crossover behaviour around room temperature with a large hysteresis loop (up to 49 K) and also display sensitivity to humidity and guest molecules. The inclusion of bpac molecules in the 3D network can be avoided by adding competitive volatile molecules during the crystallization process, affording the guest-free material. The spin crossover behavior of different guest and guest-free materials is also presented.