Self‐Assembly of a Semiconductive and Photoactive Heterobimetallic Metal–Organic Capsule

Abstract

We report the synthesis of a novel metal–organic capsule constructed from six pyrogallol[4]arene macrocycles, which are switched together by 16 FeIII and 16 CoII ions. This supramolecular structure is the first instance of a spheroidal heterometallic nanocage assembled through a one‐step metal–ligand coordination approach. This new assembly also demonstrates an important proof of concept through the formation of multiple heterometallic metal–metal interactions within the capsule framework. Photophysical and electrochemical studies of self‐assembled capsule films indicate their potential as semiconductors. These materials display unexpected photoelectric conversion properties, thus representing an emergent phenomenon in discrete metal–organic supramolecular assemblies.

A Carbonate-Templated Decanuclear Mn Nanocage with Two Different Silsesquioxane Ligands

“…Notably, the wide visible-light absorption ability and narrow band gap are the prerequisite for visible-light photocatalysis. 55 Considering the wide absorption, the photoelectrochemical properties (Figure 3c,d) of SD/ Mn10 were further tested in a typical three-electrode system by drop-casting the mixture of the solid sample with naphthol (0.5 wt % in ethanol) on indium tin oxide (ITO) glass as the working electrode, platinum wire as the assisting electrode, and Ag/AgCl as the reference electrode and keeping the bias voltage at 0.6 V (Figure S4). Under intermittent irradiation by LED light with different wavelengths (λ = 365, 420, 495, and 660 nm, respectively), unexpectedly, the film of SD/Mn10 generates strong photocurrents immediately and displays good reproducibility in both visible and UV regions.…”

Solvent‐Controlled Condensation of [Mo2O5(PTC4A)2]6− Metalloligand in Stepwise Assembly of Hexagonal and Rectangular Ag18 Nanoclusters

“…The flatband potential ( E FB ) determined by the intersection is approximately −0.58 V vs. Ag/AgCl, corresponding to a potential of −0.38 V vs. NHE. On the basis of the previous reports, the conduction band edge of the semiconductor is about 0.10 V more negative than the E FB [21] . Therefore, it can be estimated that the conduction band (LUMO) of SD/Ag18a is approximately −0.48 V vs. NHE.…”

Versatile Polymer Nanocapsules via Redox Competition

“…Hollow nanocapsules have been widely synthesized for biomedicine, energy storage, and catalysis because they provide a functional void for cargo loading and an increasingly reactive interface area [1–5] . Polymer nanocapsules with engineered size and surface chemistry are a prominent type of capsule that have been used as a viable drug delivery system and diagnostic probe due to their excellent biocompatibility [6, 7] .…”