Two Blatter Radicals Face-to-Face: A Constrained Diradical Architecture.

Cofacial arrangement of two Blatter radicals enforced by the -naphthalene scaffold represents a new approach to stable diradicals with strong through-space interactions. Two stereoisomers of the naphthalene-diradicals, and , are investigated by XRD, VT-EPR, UV-vis, electrochemical, kinetic, and DFT methods. In solutions, both stereoisomers exist as open-shell singlets with Δ = -3.

π-Curved Blatter radicals: Blatter helicenes.

Photocyclization of 8-aryloxy-3-phenylbenzo[][1,2,4]triazines leads to π-delocalized helicene radicals 1[n] ( = 5, 6, 7) containing the ring-fused 1,4-dihydro[1,2,4]triazin-4-yl as a spin source. Single crystal XRD revealed that the photocyclization to 1[n] involves a Smiles rearrangement. Radicals 1[n] were investigated by spectroscopic, electrochemical and DFT methods, while racemic helicene 1[7] was resolved and ECD spectra were recorded.

[-BH-1-CN-10-Azinium] Anions: Photoactive Heteroditopic Ligands for Metal Complexes.

A new class of rigid, photoactive heteroditopic anionic ligands based on the 1,10-disubstituted [-BH] anion was designed and six of these compounds were obtained from [-BH] in three steps with yields in the range of 25-30%. The design includes two apical substituents, a metal coordinating cyano group and an azinium (4-cyanopyridinium, 4,4'-bipyridinium, pyrazinium, pyrimidinium, and pyridazinium), which provides a secondary binding site. The azinium substituent is involved in an efficient intramolecular charge transfer process and compensates one of the two delocalized negative charges of the boron cluster.

[-BH-10-PhI-1-COOH] Anion: An Intermediate for Functional Anionic Carboxylate Ligands.

A potentially general intermediate, [-BH-10-PhI-1-COOH], for a class of functional anionic carboxylic acids, [-BH-10-X-1-COOH], was obtained in four steps and 26% overall yield from [-BH]. It was converted to the pyridinium derivative (X = CHN) and subsequently to coordination complexes with (phen)Cu and (phen)Zn ions. Both the acid and Zn(II) complex exhibit a cage-to-pyridine charge-transfer band.

Lithium salt of a pro-mesogenic [-CBH] derivative: anisotropic Li ion transport in liquid crystalline electrolytes.

Li ion conduction in two aligned liquid crystalline electrolytes consisting of 10 mol% Li salt of a pro-mesogenic anion derived from [-1-CBH] in non-ionic hosts was investigated. Using electrochemical impedance spectroscopy (EIS), the ionic conductivity in the parallel () and perpendicular () directions of the electrolyte samples was determined using two types of cells: an interdigitated gold electrode and a nylon 6-coated ITO cell. The ratio of ionic conductivities / in the electrolyte with a nona(ethylene oxide) spacer was about 3 in the entire SmA phase, while in the shorter homologue, the ratio monotonically increases from about 0.