Guest Molecules with Amino and Sulfhydryl Groups Enhance Photoluminescence by Reducing the Intermolecular Ligand-to-Metal Charge Transfer Process of Metal–Organic Frameworks

Abstract

Micron-sized metal–organic framework (MOF) sheets were prepared using organic molecules with aggregation-induced emission (AIE) properties as ligands. The intermolecular ligand-to-metal charge transfer (LMCT) process occurs in MOF structures, resulting in the disappearance of the matrix coordination-induced emission (MCIE) effect and emergence of the aggregation-caused quenching (ACQ) effect. Here, we demonstrate that molecules with electron donors can compete with the LMCT process in MOF structures, thereby changing the transfer path of the excitation energy and returning it to the ground state, mainly in the form of fluorescence. Organic molecules with amino or sulfhydryl groups can act as effective electron donors, reducing the LMCT process and causing the MCIE effect of the MOF sheet. The coexistence of amino and sulfhydryl groups will strongly inhibit the LMCT process of the MOF sheet, thereby greatly enhancing the MCIE effect. Therefore, these types of molecules can be used to regulate the photoluminescence intensity of AIE-based MOF materials. In addition, there are some organic molecules with multiple carboxyl or hydroxyl groups which can produce similar effects. Finally, it was confirmed that the intermolecular LMCT process is highly sensitive, and the MOF sheet showed distinguishable fluorescence results even with the addition of small molecules in the amount of 10−9 M. Thus, it is a feasible idea to use the fluorescence changes induced by the LMCT process as a sensitive sensing method for small molecules.

Keywords

• metal–organic framework
• aggregation-induced emission
• ligand-to-metal charge transfer
• matrix coordination-induced emission
• sensitive