Ehsan Jalilian

Size matters—sometimes. The [CuxIy](y−x)−(NR4)+(y−x) systems

A systematic study of compounds formed by solvolysis of Cu in a solution of iodine in acetol in the presence of homotetraalkylammonium iodide has resulted in five new compounds: catenatetrakis(tetramethylammonium) bis(μ3-iodo)-μ2-iodo-tri-copper(I), hexakis(tetrabutylammonium) tetrakis(μ3-iodo)-tris(μ2-iodo)-di-iodo-hexa-copper(I) pentakis(μ3-iodo)-tetrakis(μ2-iodo)-di-iodo-hepta-copper(I), tris(tetrapentylammonium) μ6-iodo-bis(μ3-iodo)-hexakis(μ2-iodo)-hexa-copper(I), hexakis(tetrahexylammonium) tetrakis(μ5-iodo)-octakis(μ2-iodo)-nona-copper(I)bis(μ5-iodo)-bis(μ4-iodo)-heptakis(μ2-iodo)-octa-copper(I) and bis(tetraheptylammonium) hexakis(μ2-iodo)-tetra-copper(I). Further the previously reported compounds catenatetraethylammonium bis(μ3-iodo)-μ2-iodo-di-copper(I) and catenatetrapropylammonium tetra(μ3-iodo)-tri-copper(I) were produced by the same method. The complexity of the cuprous iodide clusters increases with increasing chain length of the counter ion. In the system with tetraheptylammonium as counter ion, the onset of crystallization was about two years! The luminescence properties that make some cuprous iodide cluster species interesting from an applications perspective are conspicuously absent in the compounds formed with the smaller tetraalkylammonium counter ions, but the compound formed with tetraheptylammonium contains the [Cu4I6]2− unit that shows vivid luminescence when exposed to UV light.

Bis(isopropyl-triphenyl-phospho-nium) di-μ-iodido-bis-[iodidocopper(I)].

The title compound, (C21H22P)2[Cu2I4], prepared from reaction between copper powder, iodine and isopropyl triphenylphosphonium iodide in hydroxyacetone (acetol), shows an already known Cu2I4 2− anion with a planar conformation [Cu—I range = 2.5108 (3)–2.5844 (3) Å and I—Cu—I range = 110.821 (10)–125.401 (10)°].

Bis(tetraphenylphosphonium) tetraiodidomanganate(II) acetone monosolvate

The title compound, (C24H20P)2[MnI4]·(CH3)2CO, prepared from the reaction of manganese powder, iodine and tetraphenylphosphonium iodide in acetone shows a tetrahedral complex anion [Mn—I = 2.6868 (5)–2.7281 (4) Å and I—Mn—I = 104.011 (13)–116.164 (15)°], two tetraphenylphosphonium cations and one molecule of acetone.

Bis(tetra­propyl­ammonium) di-μ3-iodido-di-μ2-iodido-diiodidodi­pyridine­tetra­copper(I)

The title compound, (C12H28N)2[Cu3.194I6(C5H5N)2] was prepared from reaction of copper powder, copper(I) oxide, hydroiodic acid, tetrapropylammonium iodide and pyridine under hydrothermal conditions. In the centrosymmetric Cu4I6 2− anion, one Cu site is in a trigonal-planar coordination while the second Cu site, which is only partially occupied [site occupancy of 0.5968 (16)], is surroundedby three iodine atoms and one pyridine molecule in a distorted tetrahedral coordination.

Poly[dimethyldiphenylphosphonium [di‐μ4‐iodido‐tetra‐μ3‐iodido‐pentacopper(I)]]

The title compound, {(C(14)H(16)P)[Cu(5)I(6)]}(n), prepared from the reaction between copper powder, iodine and dimethyldiphenylphosphonium iodide in hydroxyacetone, features an anion that consists of a continuous two-dimensional Cu-I sheet [Cu-I = 2.5960 (14)-2.6994 (13) A and Cu-I-Cu = 63.28 (5)-114.25 (5) degrees]. The cation, which lies on a mirror plane, is a typical dimethyldiphenylphosphonium ion. The structure shows a strong tendency towards segregation of the inorganic and organic parts of the structure into separate subspaces. The two-dimensional Cu-I sheet displays a pronounced subcell with pseudo-tetragonal symmetry that is broken by ordered vacancies on the Cu position. The symmetry is further reduced by the orientation of the interleaved organic counter-ion that is inclined with respect to the pseudo-mirror planes defined by the Cu-I sheet normal, perpendicular to the b axis.

Poly[dimethyldiphenylphosphonium [di-mu(4)-iodido-tetra-mu(3)-iodido-pentacopper(I)]]

The title compound, {(C(14)H(16)P)[Cu(5)I(6)]}(n), prepared from the reaction between copper powder, iodine and dimethyldiphenylphosphonium iodide in hydroxyacetone, features an anion that consists of a continuous two-dimensional Cu-I sheet [Cu-I = 2.5960 (14)-2.6994 (13) A and Cu-I-Cu = 63.28 (5)-114.25 (5) degrees]. The cation, which lies on a mirror plane, is a typical dimethyldiphenylphosphonium ion. The structure shows a strong tendency towards segregation of the inorganic and organic parts of the structure into separate subspaces. The two-dimensional Cu-I sheet displays a pronounced subcell with pseudo-tetragonal symmetry that is broken by ordered vacancies on the Cu position. The symmetry is further reduced by the orientation of the interleaved organic counter-ion that is inclined with respect to the pseudo-mirror planes defined by the Cu-I sheet normal, perpendicular to the b axis.