wileyonlinelibrary.com
COMMUNICATION30 °C and every 6 h at 20 °C. Assuming an ambient temperature in the range of 20-25 °C, a suitable label should provide a clear signal to be read by the naked eye in around 3 h. [ 12 ] We here describe a new class of irreversible thermochromic molecular materials whose chemical transformation-when deposited as thin fi lms-from a colorless state to a strongly colored one depends upon temperature, chemical substitution, and substrate. The selection of the appropriate active molecule/ substrate combination provides sensitivity to different targeted time/temperature regimes, coherent with the sensitivity limits just described.The key process providing the required irreversible color change is connected with the "latent pigment" approach. [ 14 ] This process enables to induce the reversible transformation of organic pigments-like diketopyrrolopyrroles (as the red 254 pigment shown in Scheme S1 in the Supporting Information) [ 15 ] and quinacridones [ 16 ] -into soluble dyes by means of the protection of its hydrogen bond forming functionalities. As this is usually done by reaction of the pigment with ditert-butyl dicarbonate, the resulting tert-butylcarbonate ( t BOC) protection is both thermal and acid labile, with the evolution of CO 2 and isobutene (Scheme S1, Supporting Information). [ 17 ] Importantly, note that due to the involved (minor) change in the optical gap and (more importantly) aggregation state, the latent pigments are in general irreversible thermochromic materials, as we have recently shown in the context of organic solar cells. [ 15 ] Once applied to a very peculiar class of pigments-the 1,3-squaraines [ 18 ] shown in Scheme 1 , the optical gap variation associated with the latent pigment process becomes extreme, turning the blue pigment into a colorless molecule. This reaction provides the kind of dramatic color change required for smart labels directly readable by the naked eye and it is thermally irreversible (see below), thus ensuring a reliable reading by the customer. In details, Scheme 1 shows that the treatment of squaraines 1 and 2 with di-tert-butyl dicarbonate and 4-N , N -dimethylaminopyridine (DMAP) leads to the formation of betaines 3 and 4 . Since the addition of DMAP to the squarylium double bond breaks the typical cyanine conjugation of the dye, said betaines have no visible absorption. It should be noted, though, that under analogous experimental conditions, DMAP alone did not react with squaraines. Possibly, such unusual reactivity is a consequence of the severe twisting induced by the introduction of the four t BOC bulky groups in close proximity to the squarylium core. Such distortion makes the squarylium double bond more reactive toward the nucleophile addition. The pristine squarylium dye can be quantitatively recovered by thermal treatment or by addition of trifl uoroacetic acid, according to the well know acid catalyzed cleavage of t BOC groups.Food safety has always been a major concern for mankind. The wide availability of fresh perishab...