Stepwise Assembly of an Electroactive Framework from a Co₆S₈ Superatomic Metalloligand and Cuprous Iodide Building Units

Abstract

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.

Heterometallic–Organic Framework from [Cu2I2] and [PbO]n Chains: Photoluminescence, Sensing, and Photocatalytic Performance

“…As a branch of functional hybrid materials, metal–organic frameworks (MOFs), stitched together by metal centers/clusters and organic ligands with coordination bonds, have aroused great interest due to their fascinating architectures and distinct physicochemical properties such as energy storage, photoluminescence, separation, catalysis, sensing, and so on. − To prepare these functional solids with diverse networks, the utilization of secondary building units (SBUs) is considered to be an effective strategy. − As a result, numerous MOFs possessing permanent porosity and multiple properties have been constructed on the basis of various SBUs. Discrete clusters, such as the copper or silver halide based [M a X b ] a − b units, − metal carboxylate moieties − including [M 2 (COO) 4 ], [M 3 O­(COO) 6 ], and [M 4 O­(COO) 6 ], etc., are famous SBUs and have been widely employed. For instance, under the guidance of reticular chemistry proposed by Yaghi et al, the joining of a Zn 4 O­(COO) 6 SBU and similar organic linkers gives rise to a series of isoreticular MOFs bearing tunable pore shapes or sizes .…”

Synthesis and disassembly of an organometallic polymer comprising redox-active Co4S4 clusters and Janus biscarbene linkers

“…Our group is using metal chalcogenide clusters as building blocks for redox active MOF-hybrids. 33,34 This is accomplished using pre-assembled clusters stabilized with bifunctional phosphine ligands. Ancillary sites on the phosphines, and periphery of the cluster, then undergo further assembly in the presence of metal cations.…”