Synthesis and Characterization of platinum – selenium Derivatives: X-ray Structure of \u3cem\u3etrans\u3c/em\u3e-Pt(Pet\u3csub\u3e3\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3e(SePh)\u3csub\u3e2\u3c/sub\u3e

The crystal structure of trans-[((bis)triethylphosphine)(bis(phenylselenato))platinum (II)] has been determined by single crystal X-ray diffraction. Crystallization occurs in the triclinic space group P-1 (No. 2) with a = 8.9964(2) Å, b = 11.5103(2) Å, c = 14.9335(3) Å; α = 85.8750(10)°, β = 72.5350(10)°, γ = 68.4450(10)°. Details of the structure and spectroscopic results are presented and discussed and comparisons are made with related square planar platinum (II) structures

Electron Transfer Prompted Ejection of a Tightly Bound K\u3csup\u3e+\u3c/sup\u3e from the Ethereal Cavity of a Hexaarylbenzene-Based Receptor

Synthesis of a pair of rotamers (9u/9s) of a hexaarylbenzene derivative containing six (cofacially arranged) electroactive 2,5-dimethoxytolyl groups is described. The toroidal electronic stabilization due to the circular arrangement of aryl groups in 9u/9s leads to the observation of multiple (reversible) oxidation waves and lowering of their Eox1 by ∼250 mV relative to model compounds. The binding of K+ to symmetrical rotamer 9s was monitored by an electrochemical method and further confirmed by X-ray crystallography

A Shortened Synthesis of Optically Pure Tricarbonyl[methyl (2E,4E)-6-oxo-2,4-hexadienoate]Iron Leading to Improved Yield

The (+)- and (–)-enantiomers of tricarbonyl[methyl (2E,4E)-6-oxo-2,4-hexadienoate]iron are prepared in 4 steps from commercially available hexadienal (26% and 25% yields, respectively)

Bis(diethyldithiocarbamato)(iodo)(4-methoxyphenyl)tellurium(IV), \u3cem\u3ep\u3c/em\u3e-MeOC\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eTe(Et\u3csub\u3e2\u3c/sub\u3eNCS\u3csub\u3e2\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3eI, and its Isomorphous Partially Bromine-Replaced Analogue, \u3cem\u3ep\u3c/em\u3e-MeOC\u3csub\u3e6\u3c/sub\u3eH\u3csub\u3e4\u3c/sub\u3eTe(Et\u3csub\u3e2\u3c/sub\u3eNCS\u3csub\u3e2\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3eBr\u3csub\u3e0.41\u3c/sub\u3eI\u3csub\u3e0.59\u3c/sub\u3e

The structure of the title TeIV complex, C13H19BrN2OS4Te.045(CH2Cl2), is pentagonal bipyramidal with four S atoms [Te-S 2.623 (1)-2.717 (1) Å] and the Br atom [Te-Br 2.890 (1) Å] in equatorial positions. The p-methoxyphenyl group is axial [Te-C 2.145 (3) Å] and the second axial position seems to be occupied by a dithiocarbamate group of a neighbouring molecule acting as a -ligand [TeC 3.751 (3) Å, C-TeC 170.2 (1)°], so that molecules are joined into centrosymmetric associations by this secondary coordination

Hexabenzo[4.4.4]propellane: A Helical Molecular Platform for the Construction of Electroactive Materials

Helical hexabenzo[4.4.4]propellane (a relative of hexaphenylethane) and its derivatives are synthesized and their structures are established by X-ray crystallography. Isolation and X-ray crystallographic characterization of a robust trication-radical salt of hexamethoxypropellane derivative confirms that its framework is stable toward oxidative (aliphatic) C−C bond cleavage. It is also demonstrated that propellane can be easily brominated at the 4,4‘-positions of the biphenyl linkages for its usage as a molecular platform for the preparation of electroactive materials

Structural Characterization of Quaterphenyl Cation Radical: X-ray Crystallographic Evidence of Quinoidal Charge Delocalization in Poly-\u3cem\u3ep\u3c/em\u3e-phenylene Cation Radicals

Quaterphenyl derivative (QP) containing tert-butyl solubilizing groups at the terminal positions yields a stable cation radical salt that was isolated, and its structure was established by X-ray crystallography. The crystal structure of neutral QP and its cation radical (QP+•SbCl6-) provides unequivocal evidence for the quinoidal stabilization of the cationic charge or polaron by smoothing out the torsional motion of the interconnected p-phenylene rings. Such an observation of stabilization of the cationic charge in a poly-p-phenylene (PPP) derivative forms the basis for the noted high conductivities in PPP oligomers in their doped state

A Versatile Synthesis of Electroactive Stilbenoprismands for Effective Binding of Metal Cations

A versatile synthesis of a new class of polyaromatic receptors (stilbenoprismands) containing a Δ-shaped cavity similar to that of the π-prismand together with an intimately coupled electroactive stilbenoid moiety was accomplished via an efficient intramolecular McMurry coupling reaction. The presence of the Δ-shaped cavity in stilbenoprismands allows an efficient binding of a single silver cation as probed by 1H NMR spectroscopy. Electron-rich stilbenoprismands undergo a ready oxidation to their highly robust cation−radical and dicationic salts. X-ray structure determination of a representative dicationic stilbenoprismand showed that the charges were largely localized on the tetraarylethylene moiety, which results in a twisting of the ethylenic C═C bond by ∼35°. Moreover, the electronic coupling among the stilbenoid and π-prismand moieties in various stilbenoprismands was briefly probed by optical methods

A Polyaromatic Receptor with an Ethereal Fence that Directs K\u3csup\u3e+\u3c/sup\u3e for Effective Cation−π Interaction

We have designed and synthesized a HAB-based receptor with six ethereal oxygens on one face of the central benzene ring by a trimerization of a diarylacetylene in which the ethereal oxygens are tied together with a tetramethylene bridge. This unique amphiphilic receptor allows an efficient binding of a single potassium cation by a synergistic interaction with the polar ethereal fence and with the central benzene ring via cation−π interaction. Furthermore, the ready accessibility of this unique receptor with a bipolar binding pocket will allow the exploration of its usage for developing efficient sensing devices for various metal cations

Copper-Catalyzed Arylation of 1\u3cem\u3eH\u3c/em\u3e-Perfluoroalkanes

A general method has been developed for arylation of readily available 1H-perfluoroalkanes. The method employs aryl iodide and 1H-perfluoroalkane reagents, DMPU solvent, TMP2Zn base, and a copper chloride/phenanthroline catalyst. Preliminary mechanistic studies are reported