Disentangling the complex photodynamics of mixed-linker Zr-MOFs - efficient energy and charge transfer processes

Abstract

Controlling the composition, as well as the number and type of defects in metal-organic frameworks (MOFs) helps in the understanding of the interactions that govern their behaviours, and in consequence, their potential employment in a number of photonic applications. In this work, we report on the spectroscopy and photodynamics of two heterolinker (naphthalene-2,6-dicarboxylic acid, NDC, and 4-amino-8-cyanonaphthalene-2,6-dicarboxylic acid, NACDC) Zr-based MOFs that differ in the modulator used during the synthesis, thus leading to possible defects in the frameworks. We observed an inter-particle energy transfer (ET) that occurs from <10 to 160 ps in competition with an ultrafast intra-particle ET event from excited NDC to NACDC. In addition, due to the heterogeneity of the system, we found two different populations of the push-pull NACDC linker emitting from the charge transfer (CT) state. Single crystal fluorescence microscopy experiments further demostrated that the photobehavior of the studied MOFs is dominated by NACDC. Nanosecond (ns)-flash photolysis also revealed different photobehaviours related to the presence of defects, while the femtosecond (fs)-dynamics is independent of the modulators used for the MOFs’ synthesis. These results may help in engineering of MOFs for their application in photon-based science and technology and may lead to the construction of optoelectronic devices and better photocatalysts based on these materials.