Spin crossover (SCO) compounds are a very attractive type of switchable materials due to their potential application in molecular devices. Rational chemical tailoring of these switchable compounds is key for...

The search for advanced multifunctional materials displaying two or more simultaneous and correlated physicochemical properties represents a key step in developing further practical applications. In this context, here we report...

Controlled modulation of the spin-crossover (SCO) behavior through the sorption−desorption of invited molecules is an extensively exploited topic because of its potential applications in molecular sensing. For this purpose, understanding the mechanisms by which the spin-switching properties are altered by guest molecules is of paramount importance. Here, we show an experimental approach revealing a direct probe of how the interplay between SCO and host−guest chemistry is noticeably activated by chemically tuning the host structure. Thus, the axial ligand 4-phenylpyridine (4-PhPy) in the 2D Hofmann clathrates {Fe(4-PhPy) 2 [M(CN) 4 ]} (PhPyM; M = Pt, Pd) is replaced by 2,4-bipyridine (2,4-Bipy), resulting in the isomorphous compounds {Fe(2,4-Bipy) 2 [M(CN) 4 ]} (BipyM; M = Pt, Pd), which basically differ from the former in that they have a noncoordinated N heteroatom in the ancillary aromatic substituent, i.e., 2-pyridyl instead of phenyl. Our chemical, magnetic, calorimetric, and structural characterizations demonstrate that this subtle chemical composition change provokes outstanding modifications not only in the capability to adsorb small guests as water or methanol but also in the extent to which these guests affect the SCO characteristics.