Varying the frameworks of coordination polymers with (CuI)4 cubane cluster by altering terminal groups of thioether ligands

Coordination RC6H4S(CH2)8SC6H4R/(CuI)n Polymers (R (n) = H (4); Me (8)): An Innocent Methyl Group that Makes the Difference

“…This motif is unprecedented for CuX thioether adducts. To the best of our knowledge, few other examples exist, namely using the rigid ligand DABCO . Notably, the 3D MOF [ ( CuI) 7 (DABCO) 2.5 ] n built upon DABCO's linked to alternating Cu 6 I 6 and Cu 8 I 6 SBUs features Cu 8 I 8 clusters, which are very reminiscent to those found in 2 .…”

“…The Cu 8 I 8 cluster is a rather rare motif and to the best of our knowledge its chromophore properties have not been addressed . The MO representations of the frontier MOs (Figure ) indicate a distribution of the atomic contribution over the S (8.84), Cu (39.83), and I atoms (51.33%) for the HOMO (highest occupied molecular orbital) and S (3.56), Cu (50.74), and I (45.71%) for the LUMO (lowest unoccupied molecular orbital) (DFT; B3LYP, all details are in the Supporting Information).…”

Designs of 3-Dimensional Networks and MOFs Using Mono- and Polymetallic Copper(I) Secondary Building Units and Mono- and Polythioethers: Materials Based on the Cu–S Coordination Bond

“…When this acyclic ligand, 1,4-bis(benzylthio) butane, L3 reacts with CuI in a MeCN/CH 2 Cl 2 mixture in 1:1 ratio, it forms a colorless crystal of the general formula [(Cu 4 I 4 )(L3) 1.5 ] n (CSD CORYUE) [38]. This crystal exhibits a 3D framework with rare 4(6).6(4) topology.…”

Two synthetic routes to bis(1-methyl-imidazole-2-thione)methane and bis(1-benzyl-imidazole-2-thione)methane complexes including sulfur atom insertion into copper−NHC bonds

“…In this case, the SS Bn ligand coordinates via a  1 -S coordination mode for one of the sulfur donors and a μ 2 -bridging mode to two copper centres for the other sulfur donor. The copper and iodine centres form Cu4I4 cluster motifs [17] which are linked together by the SS Bn ligands. )]n where the two sulfur donors where connected to different copper centres, one sulfur donor coordinated with a  1 -S mode while the other sulfur donor bridged two copper centres.…”

“…In the structure, for each SS Bn ligand there is one copper and one iodide and the stoichiometry of the overall structure is [CuI(SS Bn )]n. Here, the copper-sulfur distances are 2.3393(17) Å for the bond involving the  1 -S coordination mode to one copper centre and 2.4136(18) Å and 2.3278(17) Å for the μ 2bridging mode to two copper centres. Finally, the structure obtained from the reaction of the copper(II) salt, Cu[BF4]2.3H2O with SS Me showed that a reduction in the oxidation state of the metal centre had occured.…”