The design of metal-organic frameworks (MOFs) that incorporate more than one metal cluster constituent is ac hallenging task. Conventionalo ne-pot reactionp rotocols requirej udiciouss election of ligand and metal ion precursors, yet remainu npredictable. Stable, preformed nanoclusters, with ligand shells that can undergo additional coordination-driven reactions, provide ap latform for assembling multi-cluster solids with precision.H erein, ad iscrete Co 6 S 8 (PTA) 6 (PTA = 1,3,5-triaza-7-phosphaadamantane) superatomic-metalloligand is assembled into a three-dimensional (3D) coordination polymer comprising Cu 4 I 4 secondary building units (SBUs). The resulting heterobimetallic framework (1)c ontains two distinct cluster constituents and bifunctional PTAl inkers. Solid-state diffuse reflectances tudies revealt hat 1 is an optical semiconductor with ab and-gap of 1.59 eV.F ramework-modified electrodes exhibit reversible redox behaviori nt he solid state arising from the Co 6 S 8 superatoms, which remain intact during framework synthesis.
We found that we can prepare atomically precise coordination polymers containing two different metal-cluster units. The way in which this material was synthesized is also noteworthy.M ost heterobimetallic frameworks are made via one-pot protocols. Our team used as tepwise approach with ad iscrete Co 6 S 8 "superatom" building block serving as the monomer.T his stable cluster remains intact during the synthesis and its redox properties are preserved after framework assembly.W eenvision that metal-chalcogenide superatoms of various composition, size, and nuclearity can be coupled with bifunctional phosphine ligands to construct as eries of multi-cluster materials using this methodology.
A double‐cluster framework comprising octahedral Co6S8 superatoms, tetrahedral Cu4I4 clusters, and 1,3,5‐triaza‐7‐phosphaadamantane (PTA) bifunctional linkers was prepared using a stepwise approach. The synthesis relies on the use of a stable, pre‐formed Co6S8(PTA)6 superatomic‐metalloligand, which can undergo further coordination‐driven assembly in the presence of CuI. The resulting three‐dimensional coordination polymer exhibits reversible redox behavior in the solid state. The artwork portrays a pair of star clusters known as the Double Cluster, which resides in the northern part of the constellation Perseus. The star clusters are 7500 light years from Earth and each contain 300 to 400 stars that can be viewed using a pair of binoculars. Illustration by Frank A. Martinez. More information can be found in the Communication by L. Wang, C. M. Bejger, et al. on page 12523.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.