Variable Cooperative Interactions in the Pressure and Thermally Induced Multistep Spin Transition in a Two-Dimensional Iron(II) Coordination Polymer.

Abstract

Two types of experiments conducted to investigate the effect of pressure on the spin crossover (SCO) properties of the 2D Fe(II) coordination polymer formulated {Fe[bipy(ttr)2]}n are reported, namely, (1) magnetic measurements performed at variable temperature and at fixed pressure and (2) visible spectroscopy at variable pressure and fixed temperature. The magnetic experiments carried out under a hydrostatic pressure constraint of 0.04, 0.08, and 0.8 GPa reveal a two-step spin transition behavior. The characteristic critical temperatures of the spin transition are shifted upward in temperature as pressure increases. The slope of the straight-line of the Tc vs P plot, dTc/dP, is 775 K/GPa and 300 K/GPa, for the high temperature and the low temperature steps, respectively. These values are remarkably large and denote the extreme sensitivity of the material to the application of pressure. Indeed, the visible spectroscopic measurements performed at 293 K show that a complete spin transition is induced at pressures as low as 0.4 GPa. Moreover, the pressure-induced spin transition is reversible and shows an asymmetric hysteresis. An analysis of the cooperative interactions of the thermal- and pressure-induced spin transition in the framework of the model of elastic interactions reveals that the elastic energy of the lattice as well as the interaction parameter between the SCO centers change during the course of the spin transition. Consequently, the character of the spin transition varies from abrupt for the high temperature step to continuous for the low temperature step.