Tetrahalidometallate(II) Ionic Liquids with More than One Metal: The Effect of Bromide versus Chloride

Fifteen N-butylpyridinium salts – five monometallic [C₄Py]₂[MBr₄] and ten bimetallic [C₄Py]₂[M_0.5^aM_0.5^bBr₄] (M=Co, Cu, Mn, Ni, Zn) – were synthesized, and their structures and thermal and electrochemical properties were studied. All the compounds are ionic liquids (ILs) with melting points between 64 and 101 °C. Powder and single-crystal X-ray diffraction show that all ILs are isostructural. The electrochemical stability windows of the ILs are between 2 and 3 V. The conductivities at room temperature are between 10⁻⁵ and 10⁻⁶ S cm⁻¹. At elevated temperatures, the conductivities reach up to 10⁻⁴ S cm⁻¹ at 70 °C. The structures and properties of the current bromide-based ILs were also compared with those of previous examples using chloride ligands, which illustrated differences and similarities between the two groups of ILs.     

Optimizing a phase gate using quantum interference

A controlled interference is proposed to reduce, by two orders of magnitude, the decoherence of a quantum gate for which the gate fidelity is limited by coupling to states other than the /0> and /1> qubit states. This phenomenon is demonstrated in an ultracold neutral atom implementation of a phase gate using qubits based on motional states in individual wells of an optical lattice.     

Collisional frequency shifts in 133Cs fountain clocks

We present a theoretical analysis of the density dependent frequency shift in Cs fountain clocks using the highly constrained binary collision model described by Leo et al. [Phys. Rev. Lett. 85, 2721 (2000)]. We predict a reversal in the clock shift at temperatures near 0.08 microK. Our results show that s waves dominate the collision process. However, as a consequence of the large scattering lengths in Cs the clock shift is strongly temperature dependent and does not reach a constant Wigner-law value until temperatures are less than 0.1 nK.     

The Synthesis of B2(SIDip)2 and its Reactivity Between the Diboracumulenic and Diborynic Extremes

A new compound with the formula L‐B₂‐L wherein the stabilizing ligand (L) is 1,3‐bis[diisopropylphenyl]‐4,5‐dihydroimidazol‐2‐ylidene (SIDip) has been synthesized, isolated, and characterized. The π‐acidity of the SIDip ligand, intermediate between the relatively non‐acidic IDip (1,3‐bis[diisopropylphenyl]imidazol‐2‐ylidene) ligand and the much more highly acidic CAAC (1‐[2,6‐diisopropylphenyl]‐3,3,5,5‐tetramethylpyrrolidin‐2‐ylidene) ligand, gives rise to a compound with spectroscopic, electrochemical, and structural properties between those of L‐B₂‐L compounds stabilized by CAAC and IDip. Reactions of all three L‐B₂‐L compounds with CO demonstrate the differences caused by their respective ligands, as the π‐acidities of the CAAC and SIDip carbenes enabled the isolation of bis(boraketene) compounds (L(OC)B‐B(CO)L), which could not be isolated from reactions with B₂(IDip)₂. However, only B₂(IDip)₂ and B₂(SIDip)₂ could be converted into bicyclic bis(boralactone) compounds.     

Rheological studies of thermosensitive triblock copolymer hydrogels

Hydrogel formation by physical cross-linking is a developing area of research toward materials suitable for pharmaceutical and biomedical applications. Polymers exhibiting lower critical solution temperature (LCST) behavior in aqueous solution are used in this study to prepare hydrogels. Four triblock copolymers (ABA) with thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) A-blocks and a hydrophilic poly(ethylene glycol) B-block have been synthesized. The molecular weight of the hydrophilic PEG block was fixed at 10 kDa, whereas the molecular weight of the pHPMAm-lactate block was varied between 10 and 20 kDa. The rheological characteristics of these polymer hydrogels were studied as a function of temperature, concentration, and the length of the thermosensitive blocks. Gelation occurred rapidly upon increasing the temperature to 37 degrees C, which makes this system suitable as an injectable formulation. The gels became stronger with increasing temperature and concentration, and moreover they behaved as critical gels, which means that G' and G' ' follow power laws over the entire frequency range. Surprisingly, with increasing length of the thermosensitive blocks, weaker hydrogels were formed. This trend can be explained by the cross-link density of the physical network, which increases with decreasing length of the thermosensitive blocks.     

Resonance fluorescence and Raman line shapes produced by monochromatic laser fields: Effects of branching ratio and homogeneous broadening

The Heitler-Ma damping theory is developed for a two level system in which the excited state is homogeneously, and irreversibly coupled to various continuum states with a total decay rate 1/τ. We give particular consideration to the channel consisting of a third, discrete, atomic level and a continuum of emitted photons, which simply corresponds to a spontaneous resonant Raman process. The theory applies to either a narrow, pulsed, laser beam, or injection of target atoms or molecules into a c.w. field.In this paper, we examine the t=∞ spectra as a function of field strength, detuning from resonance, and especially as a function of the upper state broadening, characterized by the branching ratio f_A=τ/t_A, where τ^-_A is the natural resonance fluorescence lifetime. For strong fields, we obtain the usual resonance fluorescence spectrum centered at the incident, pumping frequency, with two symmetric side bands displaced by the Rabi frequency. If f_A→0, the spectrum approaches the one-photon limit, with the height of the side bands equal to $\text{1}\text{2}$ that of the central peak and all of equal width. In this limit, the target predominantly decays into the Raman or other irreversible channels, and only a single laser photon contributes to the extremely weak resonance spectrum. At the opposite extreme, f_A→1, the target scatters many photons out of the laser-field before it is optically pumped into a non-interacting state and the spectrum exhibits the infinite cascade properties obtained by Mollow. The side bands become broadened, with a height equal to $\text{1}\text{3}$ of the central peak. In this theory, we obtain a more complete interpretation of the elastically scattered delta function, which is an artifact of the infinite lifetime of the atom in the usual two-level theories. In both limits of f_A, we obtain a Raman lineshape which is unchanged and is simply a function of the total width ?/τ of the excited state.     

Diborabutatriene: An Electron‐Deficient Cumulene

The complexation of two equivalents of a cyclic (alkyl)(amino)carbene (CAAC) to tetrabromodiborane, followed by reduction with four equivalents of sodium naphthalide, led to the formation of the CAAC‐stabilized linear diboracumulene (CAAC)₂B₂. The capacity of the CAAC ligand to facilitate B₂→CAAC donation of π‐electron density resulted in important differences between this species and a previously reported complex featuring a B?B triple bond stabilized by cyclic di(amino)carbenes, including a longer B? B bond and shorter B? C bonds. Frontier orbital analysis indicated sharing of valence electrons across the entire linear C‐B‐B‐C unit in (CAAC)₂B₂, which is supported by natural population analysis and cyclic voltammetry.     

Synthesis and Molecular Structure of trans‐[IrCl(NO)(PtBu2H)2]BF4

The synthesis and structural characterization of trans‐[IrCl(NO)(PtBu₂H)₂]BF₄ ( 1 ) is reported. The title compound was prepared in good yield in the reaction of in situ‐prepared trans‐[IrCl(coe)(PtBu₂H)₂] (coe = cis‐cyclooctene) with an appropriate amount of nitrosonium tetrafluoridoborate in dichloromethane at room temperature. Single crystals of 1 were grown from dichloromethane/diethyl ether and were analyzed by X‐ray crystallography.