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.

A 1D coordination polymer, [Zn(1,2,3-BTA)(H ₂ O)]·(H ₂ L) _0.5 ·2H ₂ O, shows superior Congo red sorption and its dye composite demonstrates significantly amplified photocurrent responses.

We herein report a fluorescent Zn(II)-supported metal–organic framework (MOF) [Zn₄(Hbpvp)₂(BTC)₃(HCOO)(H₂O)₂]·4H₂O (1) (bpvp = 3,5-bis-(2-(pyridin-4-yl)vinyl)pyridine; H₃BTC = 1,3,5-benzenetricarboxylic acid) assembled from solvothermal reactions of ZnSO₄·7H₂O with bpvp and H₃BTC ligands. Compound 1 has a unique two-dimensional (2D) layer structure and exhibits a high sensitivity and a low limit of detection of 1.0 × 10⁻⁶ mol L⁻¹ for both 2,4-dinitrophenol (2,4-DNP) and p-benzoquinone (p-BQ) in aqueous solutions, inferred from fluorescence quenching studies. The fluorescent intensity of 1 recovers upon removal of analytes, making it a promising recyclable dual-targeted luminescent probe for 2,4-DNP and p-BQ in water.

Four Cd(II) coordination polymers formulated as {[Cd₃(tpcb)₂)(η,η-μ-SO₄)₂(H₂O)₆]SO₄·16H₂O}_n (1), {[Cd(tpcb)_0.75(OH)(H₂O)₂](NO₃)}_n (2), {[Cd₂(tpcb)(SO₄)₂(H₂O)₆]·2MeOH·3H₂O}_n (3), and {[Cd(tpcb)(NO₃)(H₂O)₂](NO₃)}_n (4) were synthesized by reactions of CdSO₄ or Cd(NO₃)₂ with tetrakis(4-pyridyl)cyclobutane (tpcb) under solvothermal conditions or at ambient temperature. Compounds 1–4 were characterized by elemental analysis, IR spectroscopy, thermal analysis, powder X-ray diffraction analysis and single crystal X-ray diffraction. Compounds 1, 2, and 4 possess three different complicated 3D frameworks with the Schläfli symbols of (4⁶)(4¹²·5⁴·6⁴·8⁸), (6³)₄(6²·8⁴)₃ and (8³)(8⁶), respectively, while 3 presents a 1D chain structure. Compounds 1–4 exhibited relatively good photocatalytic activity towards the degradation of methyl orange (MO), methyl blue (MB) and rhodamine B (RhB) in aqueous solution. These results offered a good insight into the temperature effects on the assembly of Cd(II) coordination polymers and their photocatalytic applications.