Related Experiment Video
Updated: Dec 20, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Stepwise Assembly of an Electroactive Framework from a Co6 S8 Superatomic Metalloligand and Cuprous Iodide Building
Matthew B Freeman1, Ozioma D Edokobi1, Jonathan H Gillen1
1Department of Chemistry, The University of North Carolina at Charlotte, Charlotte, North Carolina, 28223, USA.
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 1.59 eV. Framework-modified electrodes exhibit reversible redox behavior in the solid state arising from the Co6 S8 superatoms, which remain intact during framework synthesis.
Related Concept Videos
Metallic Solids
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability....
Valence Bond Theory
Crystal Field Theory - Octahedral Complexes
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
Ionic Crystal Structures
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...
Formation of Complex Ions
Coordination Compounds and Nomenclature

