Extraordinary anisotropic thermal expansion in photosalient crystals

Although a plethora of metal complexes have been characterized, those having multifunctional properties are very rare. This article reports three isotypical complexes, namely [Cu(benzoate)L ₂], where L = 4-styryl-pyridine (4spy) (1), 2'-fluoro-4-styryl-pyridine (2F-4spy) (2) and 3'-fluoro-4-styryl-pyridine (3F-4spy) (3), which show photosalient behavior (photoinduced crystal mobility) while they undergo [2+2] cyclo-addition. These crystals also exhibit anisotropic thermal expansion when heated from room temperature to 200°C. The overall thermal expansion of the crystals is impressive, with the largest volumetric thermal expansion coefficients for 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10^-6 K^-1, respectively, values that are comparable to only a handful of other reported materials known to undergo colossal thermal expansion. As a result of the expansion, their single crystals occasionally move by rolling. Altogether, these materials exhibit unusual and hitherto untapped solid-state properties.