Calorimetric Investigation of Triazole-Bridged Fe(II) Spin-Crossover One-Dimensional Materials: Measuring the Cooperativity.
The relevance of abrupt magnetic and optical transitions exhibiting bistability in spin-crossover solids has been pointed out for their potential applications in optical or memory devices. In this respect, triazole-based one-dimensional coordination polymers are widely recognized as one of the most interesting systems. The measure of the interaction among spin-crossover centers at the origin of such cooperative behavior is of paramount importance and has so far been realized, through modeling of spin-crossover curves derived mostly from magnetic measurements. Here, a new series of triazole-based one-dimensional coordination polymers of formula [Fe(Rtrz)(3)](A)(2)center dot xH(2)O with R = methoxyethyl and A = monovalent anion has been prepared that show complete and abrupt spin-crossover phenomenon as shown by magnetic measurements. The spin-crossover transition in these and related compounds is studied by differential scanning calorimetry, and, the thermodynamic excess enthalpies and entropies associated with the phenomenon are derived systematically. Then the cooperative character of the spin-cross over in these materials is quantified by use of two widely used models, so-called Slichter and Drickamer and domain models. The same procedure is applied to spin-crossover curves of similar compounds available in the literature and for which calorimetric studies have been reported. The experimental thermodynamic figures, in particular the excess enthalpies, are shown to be clearly correlated to the output parameters of both models, thus providing a direct, experimental, quantitative measure of the cooperative character of the spin-crossover phenomenon.