Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature. Pyroelectric materials exhibiting large and nearly constant pyroelectric coefficients over a wide temperature range are highly desirable. Here, the authors develop molecular [FeCo] crystals with continuous pyroelectricity, originating from a transition between three distinct electronic structures.

Automated summary

The study combined molecular design and crystal engineering to obtain [FeCo] dinuclear complex crystals with unique pyroelectric behavior, with temperature dependence opposite to traditional ferroelectrics originating from a transition between three distinct electronic structures.