The reaction of the neutral dithiolene [Pd(Et2timdt)2] (Et2timdt = formally monoreduced diethylimidazolidine-2,4,5-trithione) with an excess of Br2 yielded few crystals of [1(Et) x 2Br](2+)(Br-)2(Br2)3 as a by-product (1(Et) = 4,5,9,10-tetrathiocino-[1,2-b:5,6-b']-1,3,6,8-tetraethyl-diimidazolyl-2,7-dithione); X-ray diffraction analysis showed that this compound represents the first example of a polybromide 2D-network templated by [1(Et) x 2Br](+2) dications, and featuring all the Br-Br distances shorter than those found in solid state bromine.

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The tetrabutylammonium (TBA(+)) salts of square-planar monoanionic gold complexes of the unsymmetrically substituted Ar,H-edt(2-) 1,2-dithiolene ligands (Ar,H-edt(2-)=arylethylene-1,2-dithiolato; Ar=phenyl (1(-)), 2-naphthyl (2(-)), and 1-pyrenyl (3(-))) were synthesized and characterized by spectroscopic and electrochemical methods and the corresponding neutral species (1, 2, and 3, respectively) were obtained in CH(2)Cl(2) solution at room temperature by diiodine oxidation. The single-crystal X-ray diffraction structural data collected for (TBA(+))(2(-)), supported by DFT theoretical calculations, are consistent with the ene-1,2-dithiolate form of the ligand and the Au(III) oxidation state. All complexes feature intense near-IR absorptions (at about 1.5 microm) in their neutral states and Vis-emitting properties in the 400-550 nm range, the energy of which is controlled by the charge of the complex in the case of the 3(-)/3 couple. The spectroscopic and electrochemical features of 1(x-) and 2(x-) (x=0, 1), both in their cis and trans conformations, were investigated by means of DFT and time-dependent (TD) DFT calculations.

The reactions between 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) and halogens (Br2, I2) or interhalogens (ICl, IBr) yielded different products isolated in the solid state. (Htptz+)(Br3–), (Htptz+)(IBr2–), (H3tptz3+)(I3Br4–)(IBr2–)2, and (H3tptz3+)(ICl2–)3, obtained from the reactions between tptz and Br2, IBr, and ICl, were characterized by single‐crystal X‐ray diffraction and FT‐Raman spectroscopy. All compounds are salts containing the protonated donor counterbalanced by polyhalide anions of various complexity. In particular, in (H3tptz3+)(I3Br4–)(IBr2–)2 the first example of a planar I3Br4– moiety can be observed. In the case of the reaction between tptz and I2, the elemental analysis of the product indicates a 1:1 molar ratio between tptz and I2, but the FT‐Raman spectrum is not consistent with the formation of a simple adduct, clearly indicating the simultaneous presence of diiodine and symmetric triiodide. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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