Search

The parent compound 1,3-dithiane (L1) was reacted with CuI providing the 1D coordination polymer [{Cu(μ 2 -I) 2 Cu}(μ 2 -L1) 2 ] n (CP1), an isostructural compound [{Cu(μ 2 -Br) 2 Cu}(μ 2 -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(μ 2 -Cl) 2 Cu}(μ 2 -L1)] n (CP3), in which each sulfur atom acts as a 4-electron donor. The 1D compounds [{Cu(μ 2 -X) 2 Cu}(μ 2 -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(μ 2 -I) 2 Cu}(μ 2 -L2) 2 ] n (CP5), reported previously. Using CuCN, a 2D CP of composition [{Cu(μ 2 -CN) 2 Cu}(μ 2 -L2) 2 ] n (CP9) has been isolated. Complexation of 2-isobutyl-1,3-dithiane (L3) on CuI generates a 2D material [{Cu 3 (μ 3 -I)(μ 2 -I) 2 (μ 2 -L3) 2 }] n (CP10), incorporating the usual trinuclear μ 3 -I-capped Cu clusters as SBUs, whereas 2D-polymeric compounds [{Cu(μ 2 -Br) 2 Cu}(μ 2 -L3) 2 ] n (CP11) and [{Cu(μ 2 -Cl) 2 Cu}(μ 2 -L3) 2 ] n (CP12) were obtained with CuBr and CuCl. Treatment of 2-Me 3 Si-1,3-dithiane (L4) with CuX yields the series [{Cu 2 (μ 4 -X)(μ 2 -X)}(μ 2 -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(μ 2 -I) 2 Cu}(MeCN) 2 (μ 2 -L5) 2 ] n (CP16), whereas treatment of CuI with L5 in hot EtCN yields 2D-polymeric[{Cu 3 (μ 3 -I)(μ 2 -I) 2 (μ 2 -L5) 2 }] n (CP17). A reversible phase transition from triclinic P1̅ to monoclinic P2 1 / 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(μ 2 -I) 2 Cu}(η 1 -L6) 2 (MeCN) 2 ] (D1), whereas treatment with 2 equiv of CuI affords the novel 1D CP [{Cu(μ 3 -I) 2 Cu}(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.

A structurally unique and strongly luminescent nonporous 3D coordination polymer (CP) [Cu 8 I 8 (methyldithiane) 4 ] n , CP3, has been prepared in a quasi-anticipated manner from 2-methyl-1,3-dithiane, L1, and CuI. This CP incorporates an unprecedented Cu 8 I 8 cluster built upon two side-fused open cubanes. The crystal structure of CP3 has been determined at 100, 150, 200, 250, 300, 350, and 400 K to study the temperature dependence of the Cu···Cu distances. Two other topological 1D and 2D CPs isomers of formula [{Cu 2 I 2 }(L1) 2 ] n featuring dinuclear {Cu 2 (μ 2 -I) 2 } rhomboids were also obtained independently by control of the reaction conditions. These two CPs convert into CP3 in hot PrCN, thus indicating that this latter material is the thermodynamic product. While CP1 and CP2 are not emissive, CP3 exhibits an intense luminescence due to the incorporation of the octanuclear Cu 8 I 8 clusters as secondary building units within the network. The photophysical properties of CP3 have been investigated and rationalized by means of DFT and TDDFT computing. Furthermore, the thermal stability of these materials has been studied by ATG and DSC analyses. The Raman spectra of CP1-3 have been recorded in the solid state in the 50-500 cm -1 region.