A divalent germanium complex of calix[5]arene

The reaction of the germylene Ge[N(SiMe(3))(2)](2) with calix[5]arene yields the first example of a group 14 calix[5]arene complex. The crystal structure of this material has been obtained and contains two calix[5]arene macrocycles held together by a Ge(2)O(2) rhombus.     

Fast iterative solver for convection‐diffusion systems with spectral elements

We introduce a solver and preconditioning technique based on Domain Decomposition and the Fast Diagonalization Method that can be applied to tensor product based discretizations of the steady convection–diffusion equation. The method is based on a Robin–Robin interface preconditioner coupled to a fast diagonalization solver which is used to efficiently eliminate the interior degrees of freedom and perform subsidiary subdomain solves. Using a spectral element discretization, we first apply our technique to constant wind problems, and then propose a means for applying the technique as a preconditioner for variable wind problems. We demonstrate that iteration counts are mildly dependent on changes in mesh size and convection strength. © 2009 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2011     

Surfactant addition and alternating current electrophoretic oscillation during size fractionation of nanoparticles in channels with two or three different height segments

An array of parallel planar nanochannels containing two or three segments with varying inner heights was fabricated and used for size fractionation of inorganic and biological nanoparticles. A liquid suspension of the particles was simply drawn through the nanochannels via capillary action. Using fluorescently labeled 30 nm polyacrylonitrile beads, different trapping behaviors were compared using nanochannels with 200-45 nm and 208-54-30 nm height segments. Addition of sodium dodecyl sulfate (SDS) surfactant to the liquid suspension and application of an AC electric field were shown to aid in the prevention of channel clogging. After initial particle trapping at the segment interfaces, significant particle redistribution occurred when applying a sinusoidal 8V peak-to-peak oscillating voltage with a frequency of 150 Hz and DC offset of 4V. Using the 208-54-30 nm channels, 30 nm hepatitis B virus (HBV) capsids were divided into three fractions. When the AC electric field was applied to this trapped sample, all of the virus particles passed through the interfaces and accumulated at the channel ends.     

Synthesis of monomeric Fe(II) and Ru(II) complexes of tetradentate phosphines

rac-Bis[{(diphenylphosphino)ethyl}-phenylphosphino]methane (DPPEPM) reacts with iron(II) and ruthenium(II) halides to generate complexes with folded DPPEPM coordination. The paramagnetic, five-coordinate Fe(DPPEPM)Cl(2) (1) in CD(2)Cl(2) features a tridentate binding mode as established by (31)P{(1)H} NMR spectroscopy. Crystal structure analysis of the analogous bromo complex, Fe(DPPEPM)Br(2) (2) revealed a pseudo-octahedral, cis-α geometry at iron with DPPEPM coordinated in a tetradentate fashion. However, in CD(2)Cl(2) solution, the coordination of DPPEPM in 2 is similar to that of 1 in that one of the external phosphorus atoms is dissociated resulting in a mixture of three tridentate complexes. The chloro ruthenium complex cis-Ru(κ(4)-DPPEPM)Cl(2) (3) is obtained from rac-DPPEPM and either [RuCl(2)(COD)](2) [COD = 1,5-cyclooctadiene] or RuCl(2)(PPh(3))(4). The structure of 3 in both the solid state and in CD(2)Cl(2) solution features a folded κ(4)-DPPEPM. This binding mode was also observed in cis-[Fe(κ(4)-DPPEPM)(CH(3)CN)(2)](CF(3)SO(3))(2) (4). Addition of an excess of CO to a methanolic solution of 1 results in the replacement of one of the chloride ions by CO to yield cis-[Fe(κ(4)-DPPEPM)Cl(CO)](Cl) (5). The same reaction in CH(2)Cl(2) produces a mixture of 5 and [Fe(κ(3)-DPPEPM)Cl(2)(CO)] (6) in which one of the internal phosphines has been substituted by CO. Complexes 2, 3, 4, and 5 appear to be the first structurally characterized monometallic complexes of κ(4)-DPPEPM.     

A sulfone-based strategy for the preparation of 2,4-disubstituted furan derivatives

2,4-Disubstituted furans are prepared by treating 2,3-dibromo-1-phenylsulfonyl-1-propene (DBP, 2) with 1,3-diketones under basic conditions. The furan-forming step involves a deacetylation, and the selectivity of this process depends upon the steric demand of the R group. The substituent in position 4 is elaborated by reaction of sulfonyl carbanions with alkyl halides, acyl halides, and aldehydes. Oxidative or reductive desulfonylation produces the 2,4-disubstituted furans in 60-92% yield. This strategy has been used to prepare rabdoketone A (12) and the naturally occurring nematotoxic furoic acid 13.     

Two-photon absorption properties of two-dimensional π-conjugated chromophores: combined experimental and theoretical study

The two-photon absorption (TPA) properties of four TPEB [tetrakis(phenylethynyl)benzene] derivatives (TD, para, ortho, and meta) with different donor/acceptor substitution patterns have been investigated experimentally by the femtosecond open-aperture Z-scan method and theoretically by the time-dependent density-functional theory (TDDFT) method. The four compounds show relatively large TPA cross sections, and the all-donor substituted species (TD) displays the largest TPA cross-section σ(2) = 520 ± 30 GM. On the basis of the calculated electronic structure, TD shows no TPA band in the lower energy region of the spectrum because the transition density is concentrated on particular transitions due to the high symmetry of the molecular structure. The centrosymmetric donor-acceptor TPEB para shows excitations resulting from transitions centered on D-π-D and A-π-A moieties, as well as transition between the D-π-D and A-π-A moieties; this accounts for the broad nature of the TPA bands for this compound. Calculations for two noncentrosymmetric TPEBs (ortho and meta) reveal that the diminished TPA intensities of higher-energy bands result from destructive interference between the dipolar and three-state terms. The molecular orbitals (MOs) of the TPEBs are derivable with linear combinations of the MOs of the two crossing BPEB [bis(phenylethynyl)benzene] derivatives. Overall, the characteristics of the experimental spectra are well-described based on the theoretical analysis.     

Relation between two-photon absorption and dipolar properties in a series of fluorenyl-based chromophores with electron donating or electron withdrawing substituents

We investigate two-photon absorption (2PA) in a series of fluorenyl-based 9,9-diethyl-2-ethynyl-7-((4-R-phenyl)ethynyl)-9,9a-dihydro-4aH-fluorene chromophores with R being various electron donating (ED) and electron withdrawing (EW) groups. We use wavelength-tunable femtosecond laser pulses to measure the 2PA cross sections in the lowest dipole-allowed transition and show that the substituents with stronger ED or EW character enhance the peak 2PA cross section (up to σ(2) ～ 60-80 GM) while the neutral substituents lead to smaller cross sections, σ(2) < 10 GM. We apply two-level approximation to establish a quantitative relation between the 2PA in the pure electronic transition (0-0) and the corresponding change of the permanent electric dipole moment upon the excitation (Δμ). This relation is elucidated by comparing Δμ values obtained from the 2PA measurements with quantum-chemical calculations and with measurements of solvatochromic shifts in a series of solvents. We show that the calculated Δμ correlate well with the values obtained from the 2PA spectroscopy. The Δμ values obtained from the solvatochromic shifts agree well with the above two methods for the chromophores with neutral or weak EW or ED substituents. On the other hand, stronger EW or ED end groups give much larger Stokes shifts, which lead to an overestimation of the Δμ values. We tentatively attribute this effect to the excitation-induced electronic density change occurring predominantly at the substituent side of the molecule, which causes the effective point dipole associated with the Δμ to interact more strongly with the surrounding solvent.     

The first semiquinone-bridged bisdithiazolyl radical conductor: a canted antiferromagnet displaying a spin-flop transition

The alternating ABABAB π-stacked bis-1,2,3-dithiazolyl radical 2a (2, R(2)=Ph) has a conductivity σ of 3×10(-5) S cm(-1) at 300 K, and orders as a spin-canted antiferromagnet (T(N)=4.5 K) which undergoes a spin-flop transition to a field-induced ferromagnetic state saturating (at 2 K) at H ～20 kOe.     

A light controlled cavitand wall regulates guest binding

Here we report a cavitand with a photochemical switch as one of the container walls. The azo-arene switch undergoes photoisomerization when subjected to UV light producing a self-fulfilled cavitand. This process is thermally and photochemically reversible. The reported cavitand binds small molecules and these guests can be ejected from the cavitand through this photochemical process.