Alkyne coupling at a rhenium-monocarborane substrate: synthesis of Re,B-eta2:sigma-butadienyl complexes

Treatment of 7-NH(2)Bu(t)-nido-7-CB(10)H(12) in tetrahydrofuran (THF) with LiBu(n)(3 equiv) and then [ReBr(CO)(3)(THF)(2)] gives the rhenacarborane dianion [1-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-ReCB(10)H(10)](2-), isolated as the bis-[N(PPh(3))(2)](+) salt (4). Iodine oxidation of this Re(I) intermediate gives the Re(III) complex [1,2-mu-NHBu(t)-2,2,2-(CO)(3)-closo-2,1-ReCB(10)H(10)] 6 in which the carborane functions formally as an 8-electron (6pi+ 2sigma) donor. Reaction of with ligands L in the presence of Me(3)NO gives substituted products [1,2-mu-NHBu(t)-2,2-(CO)(2)-2-L-closo-2,1-ReCB(10)H(10)][L = PPh(3)(7a), CNXyl (7b; Xyl = C(6)H(3)Me(2)-2,6), or Bu(t)C triple bond CH (7c)]. Formation of complex 7c is unexpectedly accompanied by [1,2-mu-NHBu(t)-2,2-(CO)(2)-3,2-sigma:eta(2)-{C(=CHBu(t))-CH=CHBu(t)}-closo-2,1-ReCB(10)H(9)] 8a, in which an alkyne-derived dienyl group is bound to both the rhenium centre and to an adjacent boron vertex. Complex 8a is also obtained from 7c with Bu(t)C triple bond CH and Me(3)NO. The same reaction of 7c, using PhC triple bond CH or CNXyl instead of Bu(t)C triple bond CH, gives, respectively, [1,2-micro-NHBu(t)-2,2-(CO)(2)-3,2-sigma:eta(2)-{C(=CHBu(t))-CH=CHPh}-closo-2,1-ReCB(10)H(9)] 8b and [1,2-micro-NHBu(t)-2-Bu(t)C triple bond CH-2-CO-2-CNXyl-closo-2,1-ReCB(10)H(10)] 9. Addition of donors L to results in displacement from rhenium of the pendant dienyl moiety, yielding [1,2-mu-NHBu(t)-2,2-(CO)(2)-2-L-3-{C(=CHBu(t))-CH=CHBu(t)}-closo-2,1-ReCB(10)H(9)][L = PMe(3)(10a), CNBu(t)(10b)]. Single-crystal X-ray diffraction analyses have confirmed the novel structural features of compounds 6, 7c, 8b and 9.     

Water-soluble calix[4]resorcarenes as enantioselective NMR shift reagents for aromatic compounds

A tetra L-prolinylmethyl derivative of a tetra-sulfonated calix[4]resorcarene (1) is an effective chiral NMR solvating agent for water-soluble compounds with phenyl, pyridyl, bicyclic aromatic, or indole rings. These aromatic compounds form host-guest complexes with the calix[4]resorcarene in water. Complexation of substrates with the calix[4]resorcarene is likely promoted by hydrophobic effects, and bicyclic substrates have association constants with the calix[4]resorcarene larger than those of similar phenyl-containing compounds. Aromatic resonances of the substrates show substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcarene, and several resonances in the 1H NMR spectra typically exhibit enantiomeric discrimination. The extent of enantiomeric discrimination depends in part on interactions of the substituent groups of the substrates with the prolinylmethyl groups of the calix[4]resorcarene. The effectiveness of a calix[4]resorcarene prepared from N-methyl-L-alanine (2) as a chiral NMR discriminating agent is compared to the L-prolinylmethyl derivative.     

Structure, energetics, and reactions of alkali tetramers

Electronic structure calculations have been carried out for all possible alkali tetramers that can be formed from X(2) + X(2) → X(2)X(2), X(2) + Y(2) → X(2)Y(2), and XY + XY → X(2)Y(2) alkali dimer association reactions. Vibrationally stable rhombic (D(2h)) and planar (C(s)) structures are found for all possible tetramers formed from the alkali metals, Li to Cs. All tetramer formation reactions (from ground state singlet homonuclear or heteronuclear dimers) are found to be exothermic with binding energies ranging from 6282 cm(-1) for Li(2)Li(2) to 1985 cm(-1) for Cs(2)Cs(2). Extensive calculations, carried out at long-range for several reactant pairs, indicate that there are barrier-less pathways for the formation of tetramers from dimer association reactions. At low temperatures, direct formation of tetramers is unlikely, owing to the large exothermicity associated with these association reactions, but atom exchange reactions (X(2) + Y(2) ? XY + XY) are possible for some species.     

Mixed-sequence pyrrolidine-amide oligonucleotide mimics: Boc(Z) synthesis and DNA/RNA binding properties

Pyrrolidine-amide oligonucleotide mimics (POMs) exhibit promising properties for potential applications, including in vivo DNA and RNA targeting, diagnostics and bioanalysis. Before POMs can be evaluated in these applications it is first necessary to synthesise and establish the properties of fully modified oligomers, with biologically relevant mixed sequences. Accordingly, Boc-Z-protected thyminyl, adeninyl and cytosinyl POM monomers were prepared and used in the first successful solid phase synthesis of a mixed sequence POM, Lys-TCACAACTT-NH2. UV thermal denaturation studies revealed that the POM oligomer is capable of hybridising with sequence selectivity to both complementary parallel and antiparallel RNA and DNA strands. Whilst the duplex melting temperatures (Tm) were higher than the corresponding duplexes formed with isosequential PNA, DNA and RNA oligomers the rates of association/dissociation of the mixed sequence POM with DNA/RNA targets were noticeably slower.     

Chiral molecular squares based on angular bipyridines: self-assembly, characterization, and photophysical properties

Chiral molecular squares 1-12 based on [M(dppe)](2+) metallocorners (M = Pd or Pt, and dppe = bis(diphenylphosphino)ethane) and new angular bipyridine bridging ligands derived from the 1,1'-binaphthyl framework were readily assembled and characterized by a variety of techniques including infrared, UV-vis, circular dichroism (CD), and NMR spectroscopy, and ESI mass spectrometry. All these chiral metallocycles are highly luminescent in solution at room temperature with quantum efficiency of 0.06-0.63. Interestingly, when equal molar enantiopure molecular squares of opposite handedness were mixed in solution, a new meso dimeric metallocycle with C(2) symmetry formed. This result indicates the lability of the M-pyridyl bonds in these metallocycles, which may hinder their applications in many enantioselective processes.     

Chlorometallate and palladium cluster complexes of wide-span diimine and diamine ligands

Diimine and diamine ligands that are unable to coordinate to a single metal favour the formation of unusual, high-nuclearity Zn chlorometallate and palladium chloride complexes.     

Nanoparticle-coated separators for lithium-ion batteries with advanced electrochemical performance

We report a simple, scalable approach to improve the interfacial characteristics and, thereby, the performance of commonly used polyolefin based battery separators. The nanoparticle-coated separators are synthesized by first plasma treating the membrane in oxygen to create surface anchoring groups followed by immersion into a dispersion of positively charged SiO(2) nanoparticles. The process leads to nanoparticles electrostatically adsorbed not only onto the exterior of the surface but also inside the pores of the membrane. The thickness and depth of the coatings can be fine-tuned by controlling the ζ-potential of the nanoparticles. The membranes show improved wetting to common battery electrolytes such as propylene carbonate. Cells based on the nanoparticle-coated membranes are operable even in a simple mixture of EC/PC. In contrast, an identical cell based on the pristine, untreated membrane fails to be charged even after addition of a surfactant to improve electrolyte wetting. When evaluated in a Li-ion cell using an EC/PC/DEC/VC electrolyte mixture, the nanoparticle-coated separator retains 92% of its charge capacity after 100 cycles compared to 80 and 77% for the plasma only treated and pristine membrane, respectively.     

Two dimensional laser induced fluorescence spectroscopy: a powerful technique for elucidating rovibronic structure in electronic transitions of polyatomic molecules

We demonstrate the power of high resolution, two dimensional laser induced fluorescence (2D-LIF) spectroscopy for observing rovibronic transitions of polyatomic molecules. The technique involves scanning a tunable laser over absorption features in the electronic spectrum while monitoring a segment, in our case 100 cm(-1) wide, of the dispersed fluorescence spectrum. 2D-LIF images separate features that overlap in the usual laser induced fluorescence spectrum. The technique is illustrated by application to the S(1)-S(0) transition in fluorobenzene. Images of room temperature samples show that overlap of rotational contours by sequence band structure is minimized with 2D-LIF allowing a much larger range of rotational transitions to be observed and high precision rotational constants to be extracted. A significant advantage of 2D-LIF imaging is that the rotational contours separate into their constituent branches and these can be targeted to determine the three rotational constants individually. The rotational constants determined are an order of magnitude more precise than those extracted from the analysis of the rotational contour and we find the previously determined values to be in error by as much as 5% [G. H. Kirby, Mol. Phys. 19, 289 (1970)]. Comparison with earlier ab initio calculations of the S(0) and S(1) geometries [I. Pugliesi, N. M. Tonge, and M. C. R. Cockett, J. Chem. Phys. 129, 104303 (2008)] reveals that the CCSD∕6-311G?? and RI-CC2∕def2-TZVPP levels of theory predict the rotational constants, and hence geometries, with comparable accuracy. Two ground state Fermi resonances were identified by the distinctive patterns that such resonances produce in the images. 2D-LIF imaging is demonstrated to be a sensitive method capable of detecting weak spectral features, particularly those that are otherwise hidden beneath stronger bands. The sensitivity is demonstrated by observation of the three isotopomers of fluorobenzene-d(1) in natural abundance in an image taken for a supersonically cooled sample. The ability to separate some of the (13)C isotopomers in natural abundance is also demonstrated. The equipment required to perform 2D-LIF imaging with sufficient resolution to resolve the rotational features of large polyatomics is available from commercial suppliers.