n-sigma charge-transfer interaction and molecular and electronic structural properties in the hydrogen-bonding systems consisting of p-quinone dianions and methyl alcohol

Molecular and electronic structural properties of the hydrogen-bonded complexes of p-quinone dianions (PQ(2)(-)) were investigated by electrochemistry and spectroelectrochemistry of PQ in MeCN combined with ab initio MO calculations. Hydrogen bonding between PQ(2)(-) and MeOH was measured as the continuous positive shift of the apparent second half-wave reduction potentials with increasing concentrations of MeOH. Detailed analyses of the behavior reveal that PQ(2)(-) forms the 1:2 hydrogen-bonded complexes at low concentrations of MeOH and the 1:4 complexes at high concentrations, yielding the formation constants. Temperature dependence of the formation constants allows us to yield the formation energy as 76.6 and 118.9 kJ mol(-)(1) for the 1:2 and 1:4 complex formation of the 1,4-benzoquinone dianion (BQ(2)(-)) with MeOH, respectively. These results show that the pi-dianions involving the quinone carbonyl groups exhibit very strong hydrogen-accepting ability. The longest wavelength band of the spectra of BQ(2)(-) and the chloranil dianion (CL(2)(-)) is assigned to the (1)B(3u) <-- (1)A(g) band mainly contributed from an intramolecular charge-transfer (CT) configuration. Hydrogen bonding allows the band of BQ(2)(-) and CL(2)(-) to be blue-shifted, depending on the strength of the hydrogen bonds. CNDO/S-CI calculations reveal that the blue shift is ascribed to stabilization of the ground state by the hydrogen bonding involving strong n-sigma-type CT interaction. The HF/6-31G(d) calculation results show that the structure of PQ(2)(-) is characterized by a lengthening of the C=O bonds and a benzenoid ring. The geometrical properties of the hydrogen-bonded complexes of PQ(2)(-) are a slight lengthening of the C=O bonds and a short distance of the hydrogen bonds. It is demonstrated that this situation is due to the strong n-sigma CT interaction in the hydrogen bonds. The results suggest that the differing functions and properties of biological quinones are conferred by the n-sigma CT interaction through hydrogen bonding of the dianions with their protein environment.     

Photophysical properties of borondipyrromethene analogues in solution

The photophysical properties of seven new 8-(p-substituted)phenyl analogues of 4,4-difluoro-3,5-dimethyl-8-(aryl)-4-bora-3a,4a-diaza-s-indacene (derivatives of the well-known fluorophore BODIPY) in several solvents have been studied by means of absorption and steady-state and time-resolved fluorimetry. For each compound, the fluorescence quantum yield and lifetime are lower in solvents with higher polarity owing to an increase in the rate of nonradiative deactivation. Increasing the electron withdrawing strength of the p-substituent on the phenyl group in position 8 also leads to lower fluorescence quantum yields and lifetimes. When the p-substituent on the phenyl group in position 8 is a tertiary amine [8-(4-piperidinophenyl), 8-(4-N,N-dimethylaminophenyl), and 8-(4-morpholinophenyl)], the low quantum yields of these compounds in more polar solvents can be rationalized by the inversion of the energy levels of an apolar, highly fluorescent and a polar, nonfluorescent excited state, where charge transfer from the tertiary amine to the BODIPY unit occurs. These amine analogues can be protonated at low pH in aqueous solution. Fluorescence titrations yielded pK(a) values of their conjugate ammonium salts which are in agreement with the electron donating tendency of the amine group: piperidino (4.15) > dimethylamino (2.37) > morpholino (1.47), with the pK(a) values in parentheses. The rate constant of radiative deactivation (k(f)) is the same for all compounds in all solvents studied (k(f) = 1.4 x 10(8) s(-1)).     

New carbon nanofiber/graphite felt composite for use as a catalyst support for hydrazine catalytic decomposition

Graphite felt supporting 40 nm diameter carbon nanofibers was synthesized and successfully used as a support for a high loaded iridium catalyst (30 wt%) in the decomposition of hydrazine; a strong mechanical resistance and a high thermal conductivity led to a very efficient and stable catalyst as compared to that used industrially, iridium supported on a high surface area alumina.     

S=N versus S+-N-: an experimental and theoretical charge density study

To elucidate the bonding situation in the widely discussed hypervalent sulfur nitrogen species, the charge density distributions rho(r) and related properties of four representative compounds, methyl(diimido)sulfinic acid H(NtBu)(2)SMe (1), methylene-bis(triimido)sulfonic acid H(2)C[S(NtBu)(2) (NHtBu)](2) (2), sulfurdiimide S(NtBu)(2) (3), and sulfurtriimide S(NtBu)(3) (4), were determined experimentally by high-resolution low-temperature X-ray diffraction experiments (T = 100 K). This set of molecules represents an ideal frame of reference for the comparison of SN bonding modes, because they contain short formal S=N double bonds as well as long S-N single bonds, some of them influenced by inter- or intramolecular hydrogen bonds. For comparison, the gas-phase ab initio calculations of the four model compounds, H(NMe)(2)SMe, H(2)C[S(NMe)(2)(NHMe)](2), S(NMe)(2), and S(NMe)(3), were performed. The topological features were found to be not particularly sensitive with respect to different substituents R (R = H, Me, tBu). In this paper, it is documented that theory and experiment differ in the eigenvalues of the Hessian matrix because of systematically differing positions of the bond critical points but agree very well concerning the spatial Laplacian distribution and the distinct polarization of all investigated sulfur-nitrogen bonds. Both recommend the S(+)-N(-) formulation of sulfur nitrogen bonds in 1 and 2 since all nitrogen atoms are found to be sp(3) hybridized. The planar SNx (x = 2, 3) units in the diimide 3 and the triimide 4 reveal characteristics of m-center-n-electron systems. For none of the investigated S-N bonds, a classical double bond formulation can be supported. This is further substantiated by the NBO/NRT approach. Valence expansion to more than eight electrons at the sulfur atom can definitely be excluded to explain the bonding.     

Construction of multiporphyrin arrays using ruthenium and rhodium coordination to phosphines

The synthesis of linear multiporphyrin arrays with mono- and bisphosphine-substituted porphyrins as ligand donors and ruthenium(II) or rhodium(III) porphyrins as ligand acceptors is described. With appropriate amounts of the building blocks mixed, linear dimeric and trimeric arrays have been synthesized and analyzed by (1)H NMR and (31)P NMR spectroscopy. The Ru/Rh acceptor porphyrins can be located either at the periphery or in the center of the array. Likewise, the monophosphine porphyrins can be positioned at the periphery, thus allowing a high degree of freedom in the overall composition of the arrays. This way, both donor and acceptor porphyrins can act as chain extenders or terminators. One of the trimeric complexes with two nickel and one ruthenium porphyrin has also been analyzed by X-ray crystallography. Attempts have also been made to synthesize higher order arrays by mixing appropriate amounts of the porphyrins; however, from the NMR data it cannot be concluded if monodisperse five, seven, or nine porphyrin arrays are present or if the solutions are composed of a statistical mixture of smaller and larger arrays.     

Direct quantitative determination of surface Brønsted acidity of solids by H/D exchange using D2O

A highly flexible method for direct and quantitative determination of surface Br?nsted acidity of solids in terms of number, type and strength of the acid sites based on quantitative H/D exchange kinetics between the acid solid and gaseous D2O has been developed and applied to materials covering the whole range of acidity.     

Enhanced chromatographic resolution of amine enantiomers as carbobenzyloxy derivatives in high-performance liquid chromatography and supercritical fluid chromatography

The carbobenzyloxy (cbz) protecting group is evaluated for it's potential to enhance the resolution of chiral amine enantiomers using high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). A series of cbz derivatives of commercially available racemates was prepared and analyzed by enantioselective chromatography using a variety of mobile phases and polysaccharide and Pirkle-type chiral stationary phases (CSPs). The cbz-derivatized product consistently demonstrated enhanced chiral resolution under HPLC and SFC conditions. Improved selectivity and resolution combined with an automated preparative HPLC or SFC system can lead to the rapid generation of highly purified enantiomers of desirable starting materials, intermediates or final products.     

Studies on synthesis and infrared and fluorescence spectra of new europium and terbium complexes with an amide-based open-chain crown ether

An amide-based open-chain crown ether ligand and its complexes with europium and terbium were synthesized. The complexes were characterized by elemental analysis, infrared spectra and conductivity. The europium and terbium ions were found to coordinate to the C=O oxygen atoms and pyridine nitrogen atoms. The fluorescence properties of these complexes in DMF and CH3OH/CHCl3 were studied. Under the excitation of UV light, these complexes exhibit characteristic fluorescence of europium and terbium ions. The solvent factors influencing the fluorescent intensity are discussed.     

Silicon-29 diffusion-ordered NMR spectroscopy (DOSY) as a tool for studying aqueous silicates

The first use of silicon-29 diffusion-ordered NMR spectroscopy (DOSY) is reported, in a study of the speciation of aqueous silicates.