Synthesis, structure and physical properties of the first one-dimensional phenalenyl-based neutral radical molecular conductor.

We report the preparation, crystallization, and solid-state characterization of a benzyl-substituted spirobiphenalenyl radical. The crystal structure shows that the radical is monomeric in the solid state, with the molecules packed in an unusual one-dimensional (1-D) fashion that we refer to as a pi-step stack. This particular mode of 1-D stacking is forced on the lattice arrangement by the presence of the orthogonal phenalenyl units that were specifically incorporated to prevent the crystallization of low-dimensional structures.

A stable monomeric nickel borohydride.

A stable discrete nickel borohydride complex (Tp*NiBH(4) or Tp*NiBD(4)) was prepared using the nitrogen-donor ligand hydrotris(3,5-dimethylpyrazolyl)borate (Tp*-). This complex represents one of the best characterized nickel(II) borohydrides to date. Tp*NiBH(4) and Tp*NiBD(4) are stable toward air, boiling water, and high temperatures (mp > 230 degrees C dec).

Prototypal dithiazolodithiazolyl radicals: synthesis, structures, and transport properties.

New synthetic routes to 1,2,3-dithiazolo-1,2,3-dithiazolylium salts, based on double Herz condensations of N-alkylated 2,6-diaminopyridinium salts with sulfur monochloride, have been developed. The two prototypal 1,2,3-dithiazolo-1,2,3-dithiazolyl radicals HBPMe and HBPEt have been prepared and characterized in solution by cyclic voltammetry and EPR spectroscopy. Measured electrochemical cell potentials and computed (B3LYP/6-31G) gas-phase disproportionation enthalpies favor a low on-site Coulombic repulsion energy U in the solid state.

A pi-stacked 1,2,3-dithiazolyl radical. Preparation and solid state characterization of (Cl2C3NS)(ClC2NS2).

Crystals of (Cl2C3NS)(ClC2NS2), an isothiazolyl-substituted 1,2,3-dithiazolyl radical, consist of evenly spaced, slipped pi-stacks; magnetic and conductivity measurements indicate the material is a Mott insulator with sigma RT = 2 x 10(-7) S cm-1.

Resonance-stabilized 1,2,3-dithiazolo-1,2,3-dithiazolyls as neutral pi-radical conductors.

Alkylation of the zwitterionic heterocycle 8-chloro-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridine (ClBP) with alkyl triflates affords 8-chloro-4-alkyl-4H-bis[1,2,3]dithiazolo[4,5-b:5',4'-e]pyridin-2-ium triflates [ClBPR][OTf] (R = Me, Et, Pr). Reduction of these salts with decamethylferrocene affords the corresponding ClBPR radicals as thermally stable crystalline solids. The radicals have been characterized in solution by cyclic voltammetry and EPR spectroscopy.

Magneto-opto-electronic bistability in a phenalenyl-based neutral radical.

A new organic molecular conductor, based on a spiro-biphenalenyl neutral radical, simultaneously exhibits bistability in three physical channels: electrical, optical, and magnetic. In the paramagnetic state, the unpaired electrons are located in the exterior phenalenyl units of the dimer, whereas in the diamagnetic state the electrons migrate to the interior phenalenyl units and spin pair as a pi-dimer. Against all expectations, the conductivity increases by two orders of magnitude in the diamagnetic state, and the band gap decreases.

Stacking efficiency of diselenadiazolyl pi-dimers. Consequences for electronic structure and transport properties.

The preparation and crystal structure of 5-cyanofuran-2-[1,2,3,5-diselenadiazolyl], [RCN(2)Se(2)] (R = 5-cyanofuran), is reported. Crystal data for C(6)H(2)ON(3)Se(2): monoclinic, space group P2(1), a = 7.1121(7), b= 20.

Perchlorophenalenyl radical, C13Cl9: a modulated structure with nine threefold-symmetric molecules in the asymmetric unit.

The odd-alternant perchlorophenalenyl radical, C13Cl9, forms molecular stacks centered on crystallographic threefold rotation axes, but the spacing within the stacks (3.78 A) is too large to allow good overlap of the orbitals in which the spin density is localized. The radical is ruffled because of the intramolecular repulsions between alpha Cl atoms (the Cl.

Benzo[2,1-c:3,4-c']bis(1,2,3-thiaselenazole) (BSe) and its charge trasfer chemistry. Crystal and electronic structure of [BSe]3[ClO4]2.

The S-Se-N-based heterocycle benzo[2,1-c:3,4-c']bis(1,2,3-thiaselenazole) (BSe) can be prepared by the condensation of 1,4-diaminobenzene-2,3-dithiol with selenium tetrachloride. Crystals of this compound are not isomorphous with the related benzo[2,1-c:3,4-c']bis(1,2,3-dithiazole) (BT); a structure is adopted that allows for more extensive intermolecular Se- - -Se contacts. Electro-oxidation of BSe in the presence of [n-Bu4N][ClO4] affords metallic green needles of the charge transfer salt [BSe]3[ClO4]2, which exhibit a pressed pellet conductivity sigma(RT) = 10(-1) S cm(-1).

Synthesis of bridged medium-sized rings through the intramolecular Pauson-Khand reaction.

[reaction: see text] A series of aromatic enynes containing steric buttressing elements were prepared and evaluated in the NMO-mediated Pauson-Khand cyclization. O-Allyl systems led to the expected angularly fused products, whereas the O-butenyl and O-pentenyl derivatives afforded the unprecedented bridge systems.

Dimeric phenalenyl-based neutral radical molecular conductors.

We report the preparation, crystallization, and solid-state characterization of ethyl (3)- and butyl (4)-substituted spiro-biphenalenyl radicals. Both of these compounds are found to be conducting face-to-face pi-dimers in the solid state but with different room-temperature magnetic ground states. At room temperature, 4 exists as a diamagnetic pi-dimer (interplanar separation of approximately 3.

Perchlorophenalenyl radical.

We report the preparation and solid-state characterization of the perchlorophenalenyl radical (1). The radical is initially obtained as a yellow-green solid by reduction of the perchlorophenalenium salt (12(+)). This solid sublimes in a sealed tube to give black shiny hexagonal crystals of the perchlorophenalenyl radical (1).

5,5'-Bridged bis(1,2,3-dithiazoles): spin states and charge-transfer chemistry.

Bifunctional 1,2,3-dithiazoles bridged with azine and phenylenediamine spacers have been prepared, with a view to determining the extent of communication between the two dithiazole rings as a function of the electronic and steric demands of the bridge. The crystal structure of the closed-shell diazine derivative [S(2)NClC(2)=NN=C(2)ClNS(2)] is rigorously planar. Cyclic voltammetry on this compound indicates two reversible one-electron oxidations.

trans-diaquabis(2,2'-bipyridine-N,N')-ruthenium(II) bis(hexafluorophosphate).

The Ru atom of the title complex, [Ru(C10H8N2)2-(H2O)2](PF6)2, is located on a crystallographic inversion center; the bipyridine ligands are bowed [dihedral angle between C5N planes is 162.68 (12) degrees] due to the interligand steric interactions of the trans bipyridyl units. The Ru--O distance is 2.