Secret information recorded by traditional single-encrypted invisible inks is easily cracked because the inks can switch only between “NONE” and “TRUTH”. Developing double-encrypted systems makes the information reversibly switchable between “FALSE” and “TRUTH”, which is helpful to ensure the safety of the secret information during transport. Here, we prepared heat-developed invisible inks by hydrochromic molecules donor–acceptor Stenhouse adducts (DASAs) and oxazolidines (OXs) and promoted the invisible inks from single to double encryption. DASAs coordinate with water molecules and form stable colorless cyclic DASA·xH2O molecules, which lose coordinated water molecules after heating and switch to colored linear DASAs. In contrast, OXs are colored with water and are colorless after heating. Single-encrypted secrecy was realized by DASA invisible inks. The information is invisible under the encrypted state and becomes bright purple after heating. Vapor treating re-encrypted the information in ∼5 min. Furthermore, the single-encryption was promoted to double-encryption by a DASA/OX invisible inks system. Heating and vapor treating switch the information between the “FALSE” and “TRUTH” reversibly. The DASA/OX invisible ink system is applied for secrecy of texts, graphic images, and quick response (QR) codes.

No abstract

Understanding the relationship between chemical structure and photoswitching property of donor–acceptor Stenhouse adducts (DASAs) is necessary for developments and applications of the novel photoresponsive molecule. In the current work, we demonstrated a close relationship between the length of carbon spacer and photoswitching property of DASAs. A series of DASAs with barbituric acid substituted electron-withdrawing part and N-methylaniline substituted electron-donating part were synthesized. With shortening the carbon spacer between the phenyl and amine groups in the electron-donating part, the efficiency and rate of the light-induced linear-to-cyclic isomerization are improved in all the test solvents. The molecular energy variation during the isomerization process was investigated by density functional theory calculation to further understand the mechanism. This work provides a reliable carbon spacer strategy to control the photoswitching behavior of DASAs using chemical methods.