Electrical Conductivity and Luminescence in Coordination Polymers Based on Copper(I)-Halides and Sulfur-Pyrimidine Ligands

The solvothermal reactions between pyrimidinedisulfide (pym2S2) and CuI or CuBr2 in CH2Cl2:CH3CN lead to the formation of [Cu11I7(pymS)4]n (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [CuII(μ-Br)(Br)L]2 (L = 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde) (2). In the later reaction, there is an in situ S–S, S–C(sp2), and C(sp2)–N multiple bond cleavage of the pyrimidinedisulfide resulting in the formation of 2-(pyrimidin-2-ylamino)-1,3-thiazole-4-carbaldehyde. Interestingly, similar reactions carried out just with a change in the solvent (H2O:CH3CN instead of CH2Cl2:CH3CN) give rise to the formation of coordination polymers with rather different architectures. Thus, the reaction between pym2S2 and CuI leads to the formation of [Cu3I(pymS)2]n (3) and [CuI(pym2S3)] (pym2S3 = pyrimidiltrisulfide) (4), while [Cu3Br(pymS)2]n (5) is isolated in the reaction with CuBr2. Finally, the solvothermal reactions between CuI and pyrimidine-2-thione (pymSH) in CH2Cl2:CH3CN at different ratios, 1:1 or 2:1, giv...