CuX (X = Cl, Br, I) Containing Coordination Polymers Built Upon Isomeric RSCH2Caparts per thousandCCH2SR (R = p-Tolyl, Benzyl) Dithioether Ligands: First Example of a Luminescent (CuCl)n/Dithioether Network

The CuBr salt reacts with the acetylenic dithioether 1,4-bis(p-tolylthio)but-2-yne (L1) to generate the 1D [{Cu(mu(2)-Br)(2)Cu}(mu-p-MeC6H4SCH2Ca parts per thousand CCH2SC6H4Me-p)(2)] (n) coordination polymer (1), contrasting with the previously reported reaction with CuI, which provided a 2D network [{Cu-4(mu(3)-I)(4)}(mu-p-MeC6H4SCH2Ca parts per thousand CCH2SC6H4Me-p)(2)] (n) . (JIOPM, 2014, 24, 190-200). The ribbons of 1 incorporate two different types of alternating centrosymmetric Cu(mu(2)-Br)(2)Cu rhomboids displaying loose Cu center dot center dot center dot Cu contacts of 2.9306(14) and 2.9662(14) . The reaction of CuI and CuBr with the isomeric dithioether ligand 1,4-bis(benzylthio)but-2-yne (L2) yields the isomorphous dinuclear 0D complexes [{Cu(mu(2)-X)(2)Cu}(mu-PhCH2SCH2Ca parts per thousand CCH2SCH2Ph)(2)] (2a: X = I; 2b: X = Br). These species represent the first examples of dinuclear [S-2{Cu(mu(2)-X)(2)Cu}S-2] complexes spanned by a dithioether ligand. In contrast, treatment of CuCl with L2 gives rise to the formation of an unusual 2D coordination polymer [{Cu-2(mu(2)-Cl)(mu(3)-Cl)}(mu-PhCH2SCH2Ca parts per thousand CCH2SCH2Ph)] (n) (3), in which the layers are assembled both by dative Cu-S thioether bonds and organometallic Cu-pi-acetylenic interactions via the triple bond of the L2 ligand. Furthermore, the Cu(I) centers are interconnected through mu(2)- and mu(3)-bound chloro ligands. Finally, thermal stability and photophysical proprieties were studied. This investigation demonstrated the interesting luminescent behavior of CuCl-containing coordination polymer (3).