pH‐Responsive Pillar[6]arene‐based Water‐Soluble Supramolecular Hexagonal Boxes

We describe the preparation of the first water‐soluble pH‐responsive supramolecular hexagonal boxes (SHBs) based on multiple charge‐assisted hydrogen bonds between peramino‐pillar[6]arenes 2 with the molecular “lid” mellitic acid ( 1 a ). The interaction between 2 and 1 a , as well as the other “lids” pyromellitic and trimesic acids ( 1 b and 1 c , respecively) were studied by a combination of experimental and computational methods. Interestingly, the addition of 1 a to the complexes of the protonated form of pillar[6]arene 2 , that is, 3 , with bis‐sulfonate 4 a or 4 b , immediately led to guest escape along with the formation of closed 1 a₂2 supramolecular boxes. Moreover, the process of the openning and closing of the supramolecular boxes along with threading and escaping of the guests, respectively, was found to be reversible and pH‐responsive. This study paves the way for the easy and modular preparation of different SHBs that may have myriad applications.     

Effect of molecule-metal electronic coupling on through-bond hole tunneling across metal-organic monolayer-semiconductor junctions

Using Hg/alkyl-chain-monolayer/p-Si devices we find that the type of contact between the chains and the electrodes (chemical bonding or not) is of critical importance for electronic transport across the junctions. As the semiconductor is p-type, the transport is that of holes. In agreement with theory we find that holes tunnel more efficiently through alkyl chains than do electrons.     

An algebraic approach to the morse potential scattering

A new realization of an algebra SU(1.1), associated with one-dimensional Morse oscillator is introduced. The calculation of the Morse reflection amplitude is then formulated via a recently established algebraic approach to the scattering matrix. In this approach the invariance group of the free particle, The Euclidean group, is used to describe asymptotic behaviour.     

A new proof of Poltoratskii's theorem

We provide a new simple proof to the celebrated theorem of Poltoratskii concerning ratios of Borel transforms of measures. That is, we show that for any complex Borel measure μ on and any a.e. w.r.t. μ_sing, where μ_sing is the part of μ which is singular with respect to Lebesgue measure and F denotes a Borel transform, namely, and F_μ(z)=∫(x−z)⁻¹dμ(x).     

Synthesis and reactions of some 5,6,7,8-tetrahydroquinoxaline derivatives

5,6,7,8-Tetrahydroquinoxaline derivatives containing an oxygen functionality in the 6-position were prepared by ring closure of suitable 2,3-disubstituted pyrazines such as 6 and 12 . The chemistry of these novel 5,6,7,8-tetrahydroquinoxalines is discussed.     

Ab initio characterization of C5

In this paper, the structure and spectroscopic parameters of the C5 cluster are determined using multiconfigurational quantum chemical methods as implemented in the MOLCAS software. A number of spectroscopic properties (band center positions, l-doubling parameters, and rotational constants) have been characterized. From the new results, the assignments of previous astrophysical observations [J. Goicoechea et al., Astrophys. J. 609, 225 (2004)] are discussed. A detailed exploration of the global potential energy surface confirms that C5 has a X1Sigmag+ linear isomer of prominent stability and, at least, three minimum energy structures showing singlet electronic ground states. Two of them are cyclic and one has a nonplanar geometry. Vertical and adiabatic electronic transitions and vibrational spectroscopic parameters are determined for the most stable linear isomer using multiconfigurational second order perturbation theory (CASPT2) using an active space containing 12 valence orbitals with 12 active electrons and extended ANO-type basis sets. The infrared spectrum has been analyzed from an anharmonic force field derived form the local surface, determined from the energies of a grid of 1350 geometries. The force field includes four coupling terms. The CASPT2 band center position of the nu7(piu) anharmonic fundamental has been calculated to be at 102 cm(-1), which validates the assignment to C5 of the pattern of bands centered at 102 cm(-1) observed with the ISO telescope.