Blending materials composed of boron, nitrogen and carbon to transform approaches to liquid hydrogen stores.

Mixtures of hydrogen storage materials containing the elements of boron, nitrogen, carbon, i.e., isomers of BN cyclopentanes are examined to find a 'fuel blend' that remains a liquid phase throughout hydrogen release, maximizes hydrogen storage density, minimizes impurities and remains thermally stable at ambient temperatures.

Heterolysis of H2 Across a Classical Lewis Pair, 2,6-Lutidine⋅BCl3 : Synthesis, Characterization, and Mechanism.

We report that 2,6-lutidine⋅trichloroborane (Lut⋅BCl3 ) reacts with H2 in toluene, bromobenzene, dichloromethane, and Lut solvents producing the neutral hydride, Lut⋅BHCl2 . The mechanism was modeled with density functional theory, and energies of stationary states were calculated at the G3(MP2)B3 level of theory. Lut⋅BCl3 was calculated to react with H2 and form the ion pair, [LutH(+) ][HBCl3 (-) ], with a barrier of ΔH(≠) =24.

Experimental and theoretical study of molecular response of amine bases in organic solvents.

Reorientational correlation times of various amine bases (namely, pyridine, 2,6-lutidine, 2,2,6,6-tetramethylpiperidine) and organic solvents (dichloromethane, toluene) were determined by solution-state NMR relaxation time measurements and compared with predictions from molecular dynamics (MD) simulations. The amine bases are reagents in complex reactions catalyzed by frustrated Lewis pairs (FLP), which display remarkable activity in metal-free H2 scission. The comparison of measured and simulated correlation times is a key test of the ability of recent MD and quantum electronic structure calculations to elucidate the mechanism of FLP activity.

A thermodynamic and kinetic study of the heterolytic activation of hydrogen by frustrated borane-amine Lewis pairs.

Calorimetry is used to measure the reaction enthalpies of hydrogen (H(2)) activation by 2,6-lutidine (Lut), 2,2,6,6-tetramethylpiperidine (TMP), N-methyl-2,2,6,6-tetramethylpiperidine (MeTMP), and tri-tert-butylphosphine (TBP) with tris(pentafluorophenyl)borane (BCF). At 6.6 bar H(2) the conversion of the Lewis acid Lewis base pair to the corresponding ionic pair in bromobenzene at 294 K was quantitative in under 60 min.

3-Methyl-1,2-BN-cyclopentane: a promising H2 storage material?

We provide detailed characterization of properties for 3-methyl-1,2-BN-cyclopentane 1 that are relevant to H(2) storage applications such as viscosity, thermal stability, H(2) gas stream purity, and polarity. The viscosity of 1 at room temperature is 25 ± 5 cP, about one fourth the viscosity of olive oil. TGA/MS analysis indicates that liquid carrier 1 is thermally stable at 30 °C but decomposes slowly at 50 °C.

Luminescent Diazaborolyl-Functionalized Polystyrene.

We present two different procedures for the synthesis of poly[4-(1',3'-diethyl-1',3',2'-benzodiazaborolyl)styrene] () and poly[4-(1',3'-diphenyl-1',3',2'-benzodiazaborolyl)styrene] (). The new polymers were fully characterized by GPC, multinuclear NMR, and elemental analysis. The thermal properties and stability were studied by DSC and TGA, and the optical characteristics were examined by absorption and time-resolved fluorescence spectroscopy.

Luminescent triarylborane-functionalized polystyrene: synthesis, photophysical characterization, and anion-binding studies.

A new class of highly fluorescent triarylborane polymers has been prepared from trimethylsilyl-substituted polystyrene via a modular approach that involves selective polymer modification reactions with organometallic reagents. The photophysical properties, environmental stability, and the Lewis acidity of the boron sites have been tailored through modifications in the substitution pattern on boron. The photophysical properties are indicative of electronic communication between the chromophores attached to polystyrene, which has been exploited for the efficient probing of fluoride and cyanide in the micromolar concentration range.