Carbon-13 and fluorine-19 NMR spectroscopy of the supramolecular solid p-tert-butylcalix(4)arene.alpha,alpha,alpha-trifluorotoluene

The supramolecular 1:1 host-guest inclusion compound, p-tert-butylcalix[4]arene x alpha,alpha,alpha-trifluorotoluene, 1, is characterized by 19F and 13C solid-state NMR spectroscopy. Whereas the 13C NMR spectra are easily interpreted in the context of earlier work on similar host-guest compounds, the 15F NMR spectra of solid 1 are, initially, more difficult to understand. The 19F[1H] NMR spectrum obtained under cross-polarization and magic-angle spinning conditions shows a single isotropic resonance with a significant spinning sideband manifold. The static 19F[1H] CP NMR spectrum consists of a powder pattern dominated by the contributions of the anisotropic chemical shift and the homonuclear dipolar interactions. The 19F MREV-8 experiment, which minimizes the 19F-19F dipolar contribution, helps to identify the chemical shift contribution as an axial lineshape. The full static 19F[1H] CP NMR spectrum is analysed using subspectral analysis and subsequently simulated as a function of the 19F-19F internuclear distance (D(FF) = 2.25 +/- 0.01 A) of the rapidly rotating CF3 group without including contributions from additional libration motions and the anisotropy in the scalar tensor. The shielding span is found to be 56 ppm. The width of the centerband in the 19F[1H] sample-spinning CP NMR spectrum is very sensitive to the angle between the rotor and the magnetic field. Compound 1 is thus an attractive standard for setting the magic angle for NMR probes containing a fluorine channel with a proton-decoupling facility.     

Measurement of excitation functions in the reactions 197Au(11C, xn)208-xAt using a radioactive 11C beam

A light-element radioactive ion-beam capability has been developed at the LBNL 88-Inch Cyclotron. The system is based on the coupled-cyclotrons method and utilizes short-lived species, e.g., 11C, 14O, 13N produced by (p,n) and (p,alpha) reactions at the LBNL Biomedical Isotope Facility Cyclotron. In a first experiment, 197Au(11C,xn)208-xAt excitation functions have been measured for energies ranging from the Coulomb barrier up to 110 MeV using a beam of 11C with intensities up to (1-2)x10(8) ions/sec on target. The results of this experiment are compared to measurements of 197Au(12C, xn)209-xAt excitation functions.     

Oxy-cope rearrangements of bicyclo[3.2.0]heptenones. Synthesis of bicyclo[4.2.1]non-1(4)-en-6-ones and bicyclo[5.2. 1]dec-1(10)-en-5-ones

6-exo-Methylbicyclo[3.2.0]hepten-7-ones and their 2-alkylidene analogues are readily prepared from dialkyl squarates. These compounds undergo facial oxy-Cope ring expansions upon treatment with vinyllithium; the former leads to bicyclo[4.2. 1]non-1(4)-en-6-ones and the latter to the first examples of bicyclo[5.2.1]dec-1(10)-en-5-ones, compounds having exceptionally strained bridgehead double bonds. The transformations are controlled by the 6-exo-methyl group in the starting material along with the substituent at position-1 (bridgehead) which force attack of the lithium reagent from the concave face of the starting material, thus allowing the cyclopentenyl or alkylidene groups to participate in the sigmatropic event.     

Carbon-carbon bond formation from azaallyl and imine couplings about metal-metal bonds

Typical C-C bond-forming processes feature oxidative addition, insertion, and reductive elimination reactions. An alternative strategy toward C-C bond formation involves the generation of transient radicals that can couple at or around one or more metal centers. Generation of transient azaallyl ligands that reductively couple at CH positions possessing radical character is described. Two C-C bonds form, and the redox non-innocence of the resulting pyridine-imines may be critical to formation of a third C-C bond via dinuclear di-imine oxidative coupling. Unique metal-metal bonds are a consequence of the chelation.     

Investigating the interface of superhydrophobic surfaces in contact with water

Neutron reflectivity (NR) is used to probe the solid, liquid, vapor interface of a porous superhydrophobic (SH) surface submerged in water. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160 degrees (superhydrophobic) to <10 degrees (hydrophilic). NR shows that the superhydrophobic nature of the surface prevents infiltration of water into the porous film. Atomic force microscopy and density functional theory simulations are used in combination to interpret the NR results and help establish the location, width, and nature of the SH film-water interface.     

Sweep optical frequency synthesizer with a distributed-Bragg-reflector laser injection locked by a single component of an optical frequency comb

A sweep optical frequency synthesizer is demonstrated by using a frequency-stabilized optical frequency comb and injection-locked distributed-Bragg-reflector (DBR) laser diode. The injection-locked DBR laser acts as a single-frequency filter and, simultaneously, a high-gain amplifier of the optical frequency comb. The frequency instability of the heterodyne beat signal between two independently injection-locked DBR lasers is measured to be 2.3 x 10(-16) at 1 s averaging time. The output frequency of the sweep optical frequency synthesizer can be precisely tuned over 1 GHz, and a saturated absorption spectrum of the Cs D2 line at 852 nm is recorded by the injected DBR laser.     

Synthesis and characterization of (smif)2M(n) (n = 0, M = V, Cr, Mn, Fe, Co, Ni, Ru; n = +1, M = Cr, Mn, Co, Rh, Ir; smif =1,3-di-(2-pyridyl)-2-azaallyl)

A series of Werner complexes featuring the tridentate ligand smif, that is, 1,3-di-(2-pyridyl)-2-azaallyl, have been prepared. Syntheses of (smif)(2)M (1-M; M = Cr, Fe) were accomplished via treatment of M(NSiMe(3))(2)(THF)(n) (M = Cr, n = 2; Fe, n = 1) with 2 equiv of (smif)H (1,3-di-(2-pyridyl)-2-azapropene); ortho-methylated ((o)Mesmif)(2)Fe (2-Fe) and ((o)Me(2)smif)(2)Fe (3-Fe) were similarly prepared. Metatheses of MX(2) variants with 2 equiv of Li(smif) or Na(smif) generated 1-M (M = Cr, Mn, Fe, Co, Ni, Zn, Ru). Metathesis of VCl(3)(THF)(3) with 2 Li(smif) with a reducing equiv of Na/Hg present afforded 1-V, while 2 Na(smif) and IrCl(3)(THF)(3) in the presence of NaBPh(4) gave [(smif)(2)Ir]BPh(4) (1(+)-Ir). Electrochemical experiments led to the oxidation of 1-M (M = Cr, Mn, Co) by AgOTf to produce [(smif)(2)M]OTf (1(+)-M), and treatment of Rh(2)(O(2)CCF(3))(4) with 4 equiv Na(smif) and 2 AgOTf gave 1(+)-Rh. Characterizations by NMR, EPR, and UV-vis spectroscopies, SQUID magnetometry, X-ray crystallography, and DFT calculations are presented. Intraligand (IL) transitions derived from promotion of electrons from the unique CNC(nb) (nonbonding) orbitals of the smif backbone to ligand π*-type orbitals are intense (ε ≈ 10,000-60,000 M(-1)cm(-1)), dominate the UV-visible spectra, and give crystals a metallic-looking appearance. High energy K-edge spectroscopy was used to show that the smif in 1-Cr is redox noninnocent, and its electron configuration is best described as (smif(-))(smif(2-))Cr(III); an unusual S = 1 EPR spectrum (X-band) was obtained for 1-Cr.     

Hydrogen adsorption in an interpenetrated dynamic metal-organic framework

A metal-organic framework Zn(NDC)(4,4'-Bpe)(0.5).xG [NDC = 2,6-naphthalenedicarboxylate; 4,4'-Bpe = 4,4'-trans-bis(4-pyridyl)ethylene; G = guest molecules] has been synthesized, structurally characterized, and rationalized to be a two-interpenetrated elongated primitive cubic net. Powder X-ray diffraction and adsorption studies reveal the dynamic feature of the framework, which can take up hydrogen of about 2.0 wt % at 77 K and 40 bar and 0.3 wt % at 298 K and 65 bar.