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

Abstract

The solvothermal reactions between pyrimidinedisulfide (pym(2)S(2)) and CuI or CuBr(2) in CH(2)Cl(2):CH(3)CN lead to the formation of [Cu(11)I(7)(pymS)(4)](n) (pymSH = pyrimidine-2(1H)-thione) (1) and the dimer [Cu(II)(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(sp(2)), and C(sp(2))-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 (H(2)O:CH(3)CN instead of CH(2)Cl(2):CH(3)CN) give rise to the formation of coordination polymers with rather different architectures. Thus, the reaction between pym(2)S(2) and CuI leads to the formation of [Cu(3)I(pymS)(2)](n) (3) and [CuI(pym(2)S(3))] (pym(2)S(3) = pyrimidiltrisulfide) (4), while [Cu(3)Br(pymS)(2)](n) (5) is isolated in the reaction with CuBr(2). Finally, the solvothermal reactions between CuI and pyrimidine-2-thione (pymSH) in CH(2)Cl(2):CH(3)CN at different ratios, 1:1 or 2:1, give the polymers [Cu(2)I(2)(pymSH)(2)](n) (6) and [Cu(2)I(2)(pymSH)](n) (7), respectively. The structure of the new compounds has been determined by X-ray diffraction. The studies of the physical properties of the novel coordination polymers reveal that compounds 3 and 5 present excellent electrical conductivity values at room temperature, while compounds 1, 3, and 5-7 show luminescent strong red emission at room temperature.

CuIX (X = Cl−, Br−, I−) inorganic networks separated and stabilized by a mercaptotetrazole ligand

“…The Cl3-Cu3-S1, 127.48(10)°; Cl3-Cu3-Cl3C, 121.80(12)°; S1-Cu3-Cl3C, 110.59(9)°, indicating a distorted trigonal geometry. In 1, the Cu-S, Cu-Cl and Cu-N bond lengths are basically consistent with that in other complexes [27][28][29][30][31].…”

Effect of CuI Anode Buffer Layer on the Growth of Polymers Thin Films and on the Performances of Organic Solar Cells

“…In the present study, we show that the presence of a thin CuI layer onto the ITO allows controlling the morphology of the polymer films. It has been already shown that CuI and other copper halides can interact easily with organic molecules [46][47][48][49]. For instance, complex formation between CuI and organic molecules leads to different π stacking copper halide motifs [46].…”

“…Also, it is well-established that the pymSH/pymS − and bis (2-pyrimidyl)disulfide (pym2S2) ligands are good coordinating ligands toward soft Lewis acids such as Cu (I) and it as been shown that, the solvothermal reactions between pyrimidinedisulfide (pym2S2) and CuI in CH 2 Cl 2 :CH 3 CN lead to the formation of [Cu11I7(pymS)4]n (pymSH = pyrimidine-2(1H)-thione) [47]. Another example is presented in [48] where it is shown that solution reaction of CuI and the ligand L((3-bpfob) [L: 1,3-bis(nicotinoyl) o-phenylenediamine] led to the formation of a novel coordination polymer [CuI(3-bpfob)]n that exhibited an unusual one-dimensional helical structure. All these examples show that the CuI exhibits a high tendency to react with an atom donor of organic molecules (as nitrogen, sulphur and oxygen …”

Solvothermal heterocyclic disulfide/CuX2 (X = Cl, ClO4) reactions involving dynamic S–S and C–S bond cleavage

“…They are subject to a range of reaction parameters including metal salts, solvent, temperature, and even reaction time. Compared to ambient solution reactions, hydro(solvo)thermal conditions can lead to complicated reactions of heterocyclic disulfides involving intricate rearrangements concurrent with multiple bond cleavage, sometimes resulting in totally unexpected products [20,21].…”