The parent compound 1,3-dithiane (LI) was reacted with CuI providing the 1D coordination polymer [{Cu(mu(2)-I)(2)Cu}-(mu(2) -L1)(2)](n) (CP1 ), an isostructural compound [{Cu(mu(2)-Br)(2)Cu}(mu(2)-L1)(2) (CP2) was isolated upon treatment of CuBr with LI. In contrast, treatment of LI with CuCl results in the formation of 2D polymeric [{Cu(mu(2)-Cl)(2)Cu}(mu(2)-L1)](n) (CP3), in which each sulfur atom acts as a 4-electron donor. The ID compounds [{Cu(mu(2)-X) 2Cu}(mu(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(mu(2)-I) 2 Cu}(mu(2)-L2)(2)](n) (CP5), reported previously. Using CuCN, a 2D CP of composition [{Cu(mu(2)-CN)(2)Cu}(mu(2)-L2)(2)](n) (CP9) has been isolated. Complexation of 2-isobutyl-1,3-dithiane (L3) on CuI generates a 2D material [{Cu-3(mu(3)-I)(mu(2)-I)(2) (mu(2)-L3)(2)}(n) (CP10), incorporating the usual trinuclear mu(3)-I-capped Cu clusters as SBUs, whereas 2D-polymeric compounds [{Cu(mu(2)-Br)(2)Cu}(mu(2)-L3)(2)](n) (CP11) and [{Cu(mu Cl2-)(2)Cu}(mu(2)-L3)(2)](n) (CP12) were obtained with CuBr and CuCl. Treatment of 2-Me3Si-1,3-dithiane (L4) with CuX yields the series [{Cu-2(mu(4)-X)(mu(2)-X)}(mu(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(mu(2)-I)(2)Cu}(MeCN)(2) (mu(2-)L5)(2)](n) (CP16), whereas treatment of CuI with L5 in hot EtCN yields 2D-polymericaCu(3)(mu(3)-I)(mu(2)-I)(2)(mu(2)-L5)(2)}](n) (CP17). A reversible phase transition from triclinic P (1) over bar 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(mu(2)-I)(2)Cu}(eta(1)-L6)(2) (MeCN)(2)] (D1), whereas treatment with 2 equiv of CuI affords the novel 1D CP [{Cu(mu(3)-I)(2)Cu}(mu-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.