Invisible Inks for Secrecy and Anticounterfeiting: From Single to Double-encryption by Hydrochromic Molecules.

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·HO 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.