1,3-Dithianes as Assembling Ligands for the Construction of Copper(I) Coordination Polymers. Investigation of the Impact of the RC(H)S2C3H6 Substituent and Reaction Conditions on the Architecture of the 0D-3D Networks.

The parent compound 1,3-dithiane (L1) was reacted with CuI providing the 1D coordination polymer [{Cu(μ2-I)2Cu}(μ2-L1)2] n (CP1), an isostructural compound [{Cu(μ2-Br)2Cu}(μ2-L1)2] n (CP2) was isolated upon treatment of CuBr with L1. In contrast, treatment of L1 with CuCl results in the formation of 2D polymeric [{Cu(μ2-Cl)2Cu}(μ2-L1)] n (CP3), in which each sulfur atom acts as a 4-electron donor. The 1D compounds [{Cu(μ2-X)2Cu}(μ2-L2)2] n (CP7, X = Br, and CP8, X = Cl) resulting from treatment of 2-methyl-1,3 dithiane (L2) with CuBr and CuCl are isostructural with their CuI homologue [{Cu(μ2-I)2Cu}(μ2-L2)2] n (CP5), reported previously. Using CuCN, a 2D CP of composition [{Cu(μ2-CN)2Cu}(μ2-L2)2] n (CP9) has been isolated. Complexation of 2-isobutyl-1,3-dithiane (L3) on CuI generates a 2D material [{Cu3(μ3-I)(μ2-I)2(μ2-L3)2}] n (CP10), incorporating the usual trinuclear μ3-I-capped Cu clusters as SBUs, whereas 2D-polymeric compounds [{Cu(μ2-Br)2Cu}(μ2-L3)2] n (CP11) and [{Cu(μ2-Cl)2Cu}(μ2-L3)2] n (CP12) were obtained with CuBr and CuCl. Treatment of 2-Me3Si-1,3-dithiane (L4) with CuX yields the series [{Cu2(μ4-X)(μ2-X)}(μ2-L4)] n (CP13-CP15). With 2-phenyl-1,3-dithiane (L5), the outcome of the reaction with CuI depends on the reaction conditions. Reaction with CuI in MeCN provides a 1D ribbon [{Cu(μ2-I)2Cu}(MeCN)2(μ2-L5)2] n (CP16), whereas treatment of CuI with L5 in hot EtCN yields 2D-polymeric[{Cu3(μ3-I)(μ2-I)2(μ2-L5)2}] n (CP17). A reversible phase transition from triclinic P1̅ to monoclinic P21/ m is observed when recording the structure of CP16 at five different temperatures in the 100-300 K range. Ligand L6 containing a ferrocenyl function at the 2-position was also probed as organometallic dithioether ligand. Reaction of L6 with 1 equiv of CuI produces the 0D dinuclear complex [{Cu(μ2-I)2Cu}(η1-L6)2(MeCN)2] (D1), whereas treatment with 2 equiv of CuI affords the novel 1D CP [{Cu(μ3-I)2Cu}(μ-L6)] n (CP18), in which both S atoms of one L6 molecule span two copper centers of the infinite (CuI) n ribbon. Some selected results of thermal analyses and luminescence measurements are also presented.