Blue luminescent N,S-doped carbon dots encapsulated in red emissive Eu-MOF to form dually emissive composite for reversible anti-counterfeit ink.

Abstract

Lanthanide metal-organic frameworks (Ln-MOFs) have demonstrated great potential in luminescence sensing and optical anti-counterfeiting. High-security anti-counterfeiting technology is of great importance and requires the development of universal luminescent materials with multiple modes of emission and adjustable photoluminescence. Herein, a 3D red light emission microporous europium(iii) metal-organic framework [Eu3(OH)(1,3-db)2(H2O)4]·3H2O (1) (1,3-db = 1,3-di(3',5'-dicarboxylpheny) benzene) was constructed from a zigzag [Eu3(COO)8] chain and π-electron-rich terphenyl-tetracarboxylate. Notably, the quenched fluorescence of 1 under hydrogen chloride vapor could be recovered upon fuming by a vapor of Et3N. Most strikingly, the strong blue light emission by nitrogen and sulfur co-doped carbon dots (N,S-CDs) could be encapsulated in 1 to generate a dual-emission composite, namely, N,S-CDs@Eu-MOF, which shows solvent-dependent photoluminescence: N,S-CD-related blue luminescence in water and Eu-MOF-related red emission in organic solvents. Taking advantage of the above unique reversible fluorescent behavior, Eu-MOF and N,S-CDs@Eu-MOF are prepared as fluorescent high-security inks to achieve data encryption and decryption on specific flower patterns.