Engineering Flexible Metal‐Phenolic Networks with Guest Responsiveness via Intermolecular Interactions

Abstract

Flexible metal‐organic materials are of growing interest owing to their ability to undergo reversible structural transformations under external stimuli. Here, we report flexible metal‐phenolic networks (MPNs) featuring stimuli‐responsive behavior to diverse solute guests. The competitive coordination of metal ions to phenolic ligands of multiple coordination sites and solute guests (e.g., glucose) primarily determines the responsive behavior of the MPNs, as revealed experimentally and computationally. Glucose molecules can be embedded into the dynamic MPNs upon mixing, leading to the reconfiguration of the metal‐organic networks and thus changes in their physicochemical properties for targeting applications. This study expands the library of stimuli‐responsive flexible metal‐organic materials and the understanding of intermolecular interactions between metal‐organic materials and solute guests, which is essential for the rational design of responsive materials for various applications.

An Encyclopedic Compendium on Chemosensing Supramolecular Metal‐Organic Gels

“…Another avenue is the incorporation of functional metalphenolic materials [290] or flexible metal-phenolic networks (MPNs) with stimuli-responsive behavior towards various guests. [291] Their antimicrobial applications [292] can be explored as biomedical coating materials. [293] Myriad gelators scaffolds are available based on phenolic, [294] amide functionality [295] or carboxylate moeity, [296] acylhydrazone, [297] nucleoside: [298] guanosine, [299] sugar, [300] Schiff base, [301] naphthalene diimide, [302] bis(L-Leu-oxalamide), [303] bis(amino alcohol)oxalamide, [304,305] bisphenol A, [306] 1,3 : 2,4-dibenzylidenesorbitol, [307] barbiturate [308] amino acids viz.…”

“…halogen bonding, [287] metallophilic interactions as a mediator [288,289] can be harnessed. Another avenue is the incorporation of functional metal–phenolic materials [290] or flexible metal‐phenolic networks (MPNs) with stimuli‐responsive behavior towards various guests [291] . Their antimicrobial applications [292] can be explored as biomedical coating materials [293] .…”

Functional metal-phenolic cortical cytoskeleton for artificial cells

“…Benefiting from the inherent properties of MPNs (34)(35)(36)(37)(38)(39)46), our artificial cortical cytoskeleton confers artificial cells various functional abilities. For example, TA-Fe(III) complex can absorb ultraviolet (UV) light (35,46,47), so we envisage that LMPCC should show anti-UV properties.…”

“…Here, we introduce a metal-phenolic cortical cytoskeleton for stabilizing and shaping liposome-based artificial cells. Metal-phenolic networks (MPNs) are supramolecular coordination structures of metal ions and polyphenols (33) and have a myriad of advantages such as easy fabrication, high mechanical strength, outstanding biocompatibility, promising theragnostic applications, and tunable permeability (33)(34)(35)(36)(37)(38)(39). MPNs have been applied as cell-like compartments and cell coatings (40)(41)(42)(43) and are outstanding candidates for artificial cortical cytoskeletons to improve the stability of the liposome-based artificial cells.…”