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.

Keggin-Type Tridecanuclear Europium-Oxo Nanocluster Protected by Silsesquioxanes

“…Thus, the flat band potential is obtained to be −0.95 V versus normal hydrogen electrode (NHE), and the conduction band edge lowest unoccupied molecular orbital is more negative by about 0.1 V (−1.05 V). 71,72 Based on the band gap as described above, the valence band highest occupied molecular orbital can be calculated to be 2.15 V versus NHE. The film also displays a fast and stable photocurrent response to each on-off event under both visible and UV excitation, indicating that the Eu13/ITO can be photoexcited, and photogenerated carriers can be efficiently transported with the function of ITO.…”

Impact of flexible succinate connectors on the formation of tetrasulfonylcalix[4]arene based nano-sized polynuclear cages: structural diversity and induced chirality study

“…The controlled formation, in self-assembly conditions, of coordination compounds tunable different shape and size may be achieved within the ligand scaffold, by pointing the coordinating sites in preorganized fashion, for example. In this respect, the use of macrocyclic compounds of the metacyclophane family 9,10 is a powerful tool to grow large coordination capsules, due to their unlimited possibilities of functionalization of the metacyclophane moiety. Among the accessible metacyclophanes, one should mention the calix[4]arene 11 (1-4H, figure 1) and, especially, thiacalix[4]arene 12 (2-4H, figure 1) as well as tetrasulfonylcalix[4]arene 13,14 (3-4H, figure 1) based polydentate macrocyclic ligands, owing to the preorganized orientation of the coordinating sites, when adopting their cone conformation.…”