Exploiting Supramolecular Dynamics in Metal–Phenolic Networks to Generate Metal–Oxide and Metal–Carbon Networks

Abstract

Supramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal–phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their diverse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal–oxide networks (MONs) and metal–carbon networks, respectively. Furthermore, by integrating photo‐responsive motifs (i.e., TiO2) and silanization, the MONs are endowed with reversible superhydrophobic (>150°) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into diverse materials, this work offers a versatile pathway for advanced materials engineering.

Molecular design of heterogeneous electrocatalysts using tannic acid-derived metal–phenolic networks

“…It is well-known that ligand-to-metal charge transfer (LMCT) can take place between phenolic groups and metal ions in MPNs. 41,42 This suggests that the catalytic efficiency of MPNs and MPN-based hybrid systems can be further improved by enhancing the charge separation and reducing the charge recombination via the LMCT process from the LUMO of phenolic groups to metal ions in MPNs (Fig. 2d).…”

A platinum@polymer-catechol nanobraker enables radio-immunotherapy for crippling melanoma tumorigenesis, angiogenesis, and radioresistance

“…Natural or synthetic polyphenols are prevalent compounds for metal-coordination or noble metal reductants, and the oxidized polyphenols can serve as capping reagents to form and stabilize programmable nanocages. The feasible redox between diverse metals with high reduction potentials and phenolic donors endows nanocages with pleiotropic properties, including excellent biocompatibility and convenient manipulation [ [24] , [25] , [26] , [27] , [28] ]. Here, we tactfully designed a mTOR inhibitor TAK228-loaded aPD-L1-enriched platinum-based three-pronged platinum@polymer-catechol nanobraker (aPD-L1-Pt@TAK228@PEG-polyphenol, denoted as APTP NPs) with radio-reinforced tumoridical-immunity for dampening melanoma intrinsic PD-1:PD-L1 protumorigenic signaling and enhancing the melanoma eradication ( Fig.…”