Stepwise Assembly of an Electroactive Framework from a Co6 S8 Superatomic Metalloligand and Cuprous Iodide Building Units.
Chemistry
; 26(55): 12523-12527, 2020 Oct 01.
Article
em En
| MEDLINE
| ID: mdl-32441378
ABSTRACT
The design of metal-organic frameworks (MOFs) that incorporate more than one metal cluster constituent is a challenging task. Conventional one-pot reaction protocols require judicious selection of ligand and metal ion precursors, yet remain unpredictable. Stable, preformed nanoclusters, with ligand shells that can undergo additional coordination-driven reactions, provide a platform for assembling multi-cluster solids with precision. Herein, a discrete Co6 S8 (PTA)6 (PTA=1,3,5-triaza-7-phosphaadamantane) superatomic-metalloligand is assembled into a three-dimensional (3D) coordination polymer comprising Cu4 I4 secondary building units (SBUs). The resulting heterobimetallic framework (1) contains two distinct cluster constituents and bifunctional PTA linkers. Solid-state diffuse reflectance studies reveal that 1 is an optical semiconductor with a band-gap of 1.59â
eV. Framework-modified electrodes exhibit reversible redox behavior in the solid state arising from the Co6 S8 superatoms, which remain intact during framework synthesis.
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MEDLINE
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2020
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Article