Rational construction of functional molybdenum (tungsten)–copper–sulfur coordination oligomers and polymers from preformed cluster precursors
- 13 May 2016
- journal article
- review article
- Published by Royal Society of Chemistry (RSC) in Chemical Society Reviews
- Vol. 45 (18), 4995-5019
- https://doi.org/10.1039/c6cs00096g
Abstract
The investigation of heterometallic Mo(W)–M′–S clusters (M′ = transition metals) has its genesis in the late 1970s with the identification of the nitrogenase iron–molybdenum cofactor (FeMoco) featuring a Mo–Fe–S double-cubane cluster core. This has led to the generation of a library of cluster skeletons subsequently used as building blocks for oligomers (OGs) and polymers, merging this field with the fascinating developments in supramolecular chemistry and coordination polymers (CPs). While resembling the general metal–ligand assembly to form CPs in one-pot, cluster-based OGs or CPs are conventionally prepared from Mo(W)–S synthons and Cu(I) salts in the presence of bridging ligands. This review summarizes the synthesis of Mo(W)–Cu–S cluster-supported OGs and CPs through a two-step strategy involving preformed clusters. This stepwise approach facilitates clean conversion, and is amenable to exquisite design protocols and yields products otherwise inaccessible via a direct one-pot method. We review the synthesis of OGs and CPs by cluster core upgrading, downgrading, ligand substitution, and cluster aggregation reactions, together with the optical and host–guest properties of the products. In doing so, we demonstrate the power and generality of this strategy for assembling these unique materials and offer clues on how to adapt this less practiced method to preparing extended molecular assemblies with potentially intriguing properties.Keywords
Funding Information
- National Natural Science Foundation of China (21373142, 21401134, 21531006)
This publication has 100 references indexed in Scilit:
- Cp*Rh-Based Heterometallic Metallarectangles: Size-Dependent Borromean Link Structures and Catalytic Acyl TransferJournal of the American Chemical Society, 2013
- Iodine Release and Recovery, Influence of Polyiodide Anions on Electrical Conductivity and Nonlinear Optical Activity in an Interdigitated and Interpenetrated Bipillared-Bilayer Metal–Organic FrameworkJournal of the American Chemical Society, 2012
- Metal Azolate Frameworks: From Crystal Engineering to Functional MaterialsChemical Reviews, 2011
- The [MoFe3S4]2+ Oxidation State: Synthesis, Substitution Reactions, and Structures of Phosphine-Ligated Cubane-Type Clusters with the S = 2 Ground StateInorganic Chemistry, 2011
- Monomeric, Dimeric and Polymeric W/Cu/S Clusters Based on [Et4N][Tp*W(μ3-S)3(CuBr)3] and Various Nitrogen Donor LigandsInorganic Chemistry, 2009
- Structural Conversions of Molybdenum−Iron−Sulfur Edge-Bridged Double Cubanes and PN-Type Clusters Topologically Related to the Nitrogenase P-ClusterInorganic Chemistry, 2003
- Synthesis of a Molecular Mo2Fe6S9 Cluster with the Topology of the PN Cluster of Nitrogenase by Rearrangement of an Edge-Bridged Mo2Fe6S8 Double CubaneJournal of the American Chemical Society, 2003
- Probing two-photon excitation dynamics using ultrafast laser pulsesOptics Communications, 1998
- Structure−Function Relationships of Alternative NitrogenasesChemical Reviews, 1996
- On the Synthesis of the FeMo Cofactor of Nitrogenase: Gene‐Controlled in Nature versus Laboratory‐Produced by ManAngewandte Chemie-International Edition, 1995