Redox-Controlled Self-Assembly of Vanadium-Seamed Hexameric Pyrogallol[4]Arene Nanocapsules

Xiangquan Hu; Wenjuan Tian; Yuan Jiao; Steven P Kelley; Ping Wang; Scott J Dalgarno; David A Atwood; Sisi Feng; Jerry L Atwood

doi:10.1021/jacs.3c05448

Redox-Controlled Self-Assembly of Vanadium-Seamed Hexameric Pyrogallol[4]Arene Nanocapsules

J Am Chem Soc. 2023 Sep 20;145(37):20375-20380. doi: 10.1021/jacs.3c05448. Epub 2023 Sep 6.

Authors

Xiangquan Hu¹, Wenjuan Tian², Yuan Jiao², Steven P Kelley¹, Ping Wang³, Scott J Dalgarno⁴, David A Atwood⁵, Sisi Feng^{2

6}, Jerry L Atwood¹

Affiliations

¹ Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri 65211, United States.
² Key Laboratory of Chemical Biology, Molecular Engineering of Ministry of Education, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China.
³ School of Chemical Sciences, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.
⁴ Institute of Chemical Sciences, Heriot-Watt University, Riccarton, Edinburgh EH14 4AS, United Kingdom.
⁵ Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506, United States.
⁶ Institute of Carbon-Based Thin Film Electronics, Peking University, Shanxi, Taiyuan 030012, China.

PMID: 37672654
DOI: 10.1021/jacs.3c05448

Abstract

Here we report the controlled self-assembly of vanadium-seamed metal-organic nanocapsules with specific metal oxidation state distributions. Three supramolecular assemblies composed of the same numbers of components including 24 metal centers and six pyrogallol[4]arene ligands were constructed: a V^III₂₄L₆ capsule, a mixed-valence V^III₁₈V^IV₆L₆ capsule, and a V^IV₂₄L₆ capsule. Crystallographic studies of the new capsules reveal their remarkable structural complexity and geometries, while marked differences in metal oxidation state distribution greatly affect the photoelectric conversion properties of these assemblies. This work therefore represents a significant step forward in the construction of intricate metal-organic architectures with tailored structure and functionality.