Visible light-mediated supramolecular framework for tunable CO2 adsorption

Abstract

In the pursuit of creating azobenzene-functionalized photo-responsive supramolecular frameworks (PSMFs) activated by the visible spectrum, an endeavor traditionally relied on ultraviolet activation, we report the successful fabrication of a visible light-mediated metal–organic cage-based PSMF, designated as NUT-104. This achievement was realized by the hierarchical self-assembly process of Zr-metal–organic cages featuring ortho-fluoroazobenzene functional terephthalic acid and tri-nuclear Zr-clusters. NUT-104 displays permanent porosity coupled with reversible responsiveness to visible light. This remarkable behavior emerges as a consequence of the σ-electron-withdrawing effect induced by the presence of fluorine substituents. Visible light-regulated CO2 adsorption capacity can be achieved and the change value can reach 61 %, while the change for CH4 and N2 is only 7 % and 3 %, respectively. In response to irradiation at wavelengths of 520 and 420 nm, respectively, the azobenzene moieties within the NUT-104 structure exhibit a remarkable capacity for visible light-controlled reversible conformational changes. Grand Canonical Monte Carlo simulations unveiled that the dynamic reorganization of the NUT-104 proficiently governs the accessibility of CO2 adsorption sites positioned within the interstitial regions of proximate cages. The advent of NUT-104, underpinned by its visible light responsiveness and versatile tunability, paves the way for avenues of exploration in controlled gas separation and storage applications.