Compressing a Non-Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene

This work describes a synthetic approach where a non-planar aromatic heterocyclic [7]helicene is compressed to yield a hetero[8]circulene containing an inner antiaromatic cyclooctatetraene (COT) core. This [8]circulene consists of four benzene rings and four heterocyclic rings, and it is the first heterocyclic [8]circulene containing three different heteroatoms. The synthetic pathway proceeds via a the flattened dehydro-hetero[7]helicene, which is partially a helicene and partially a circulene: it is non-planar and helically chiral as helicenes, and contains a COT motif like [8]circulenes. The antiaromaticity of the COT core is confirmed by nucleus independent chemical shift (NICS) calculations. The planarization from a helically π-conjugated [7]helicene to a fully planar heterocyclic [8]circulene significantly alters the spectroscopic properties of the molecules. Post-functionalization of the [7]helicenes and the [8]circulenes by oxygenation of the thiophene rings to the corresponding thiophene-sulfones allows an almost complete fluorescence emission coverage of the visible region of the optical spectrum (400–700 nm).     

Regioselective Hydroformylation of Internal and Terminal Alkenes via Remote Supramolecular Control

Regioselective catalytic transformations using supramolecular directing groups are increasingly popular as it allows for control over challenging reactions that may otherwise be impossible. In most examples the reactive group and the directing group are close to each other and/or the linker between the directing group is very rigid. Achieving control over the regioselectivity using a remote directing group with a flexible linker is significantly more challenging due to the large conformational freedom of such substrates. Herein, we report the redesign of a supramolecular Rh–bisphosphite hydroformylation catalyst containing a neutral carboxylate receptor (DIM pocket) with a larger distance between the phosphite metal binding moieties and the DIM pocket. For the first time regioselective conversion of internal and terminal alkenes containing a remote carboxylate directing group is demonstrated. For carboxylate substrates that possess an internal double bond at the Δ-9 position regioselectivity is observed. As such, the catalyst was used to hydroformylate natural monounsaturated fatty acids (MUFAs) in a regioselective fashion, forming of an excess of the 10-formyl product (10-formyl/9-formyl product ratio of 2.51), which is the first report of a regioselective hydroformylation reaction of such substrates.     

Analytical comparison between the surface current integral equation and the second-order small-slope approximation

This paper is the third in a series discussing a new approximate bistatic model for electromagnetic scattering from perfectly conducting rough surfaces. Our previous approach supplemented the Kirchhoff model through the addition of new terms involving linear orders in slope and surface elevation differences that arise naturally from a second iteration of the surface current integral equation. This completion of the Kirchhoff was shown to provide the correct first-order small perturbation method (SPM-1) in the general bistatic context. The agreement with SPM-1 was achieved because differences of surface heights are no longer expanded in powers of surface slope. While consistent with SPM, our previous formulation fails to reconverge toward the Kirchhoff model, at some incidence and scattered angles, when the illuminated surface satisfies the high frequency roughness condition. This weakness is also shared with the first-order small slope approximation (SSA-1) which is structurally equivalent to our previous formulation where the polarization is independent of surface roughness. The second-order small slope approximation (SSA-2), which satisfies the SPM-1 and second-order small perturbation method (SPM-2) limits by construction, was shown by Voronovich to converge toward the tangent plane approximation of the Kirchhoff model under high frequency conditions. In the present paper, we show that, in addition to the linear orders in our previous model, one must now include cross-terms between slope and surface elevation to ensure convergence toward both high frequency and small perturbation limits. With the inclusion of these terms, our new formulation becomes comparable to the SSA-2 (second-order kernel) without the need to evaluate all the quadratic order slope and elevations terms. SSA-2 is more complete, however, in the sense that it guarantees convergence toward the second-order Bragg limit (SPM-2) in the fully dielectric case in addition to both SPM-1 and Kirchhoff. Our new generalization is shown to explain correctly extra depolarization in specular conditions to be caused by surface curvature and surface autocorrelation for incoherent and coherent scattering, respectively. This result will have large repercussions on the interpretation of bistatically reflected signals such as those from GPS.     

The weak tail dependence coefficient of the elliptical generalized hyperbolic distribution

The strong and the weak tail dependence coefficients are measures that quantify the probability of conjoint extreme events of two random variables. Whereas formulas for both tail dependence coefficients exist for the Gaussian and Student t distribution, only the strong tail dependence coefficient is known for their super-model, the elliptical generalized hyperbolic distribution, which is extremely popular in finance (see Schmidt 2003). In this work we derive a simple expression for the corresponding weak tail dependence coefficient using the mixture representation of the elliptical generalized hyperbolic distribution.     

Different Faces of the Shearlet Group

Recently, shearlet groups have received much attention in connection with shearlet transforms applied for orientation sensitive image analysis and restoration. The square integrable representations of the shearlet groups provide not only the basis for the shearlet transforms but also for a very natural definition of scales of smoothness spaces, called shearlet coorbit spaces. The aim of this paper is twofold: first we discover isomorphisms between shearlet groups and other well-known groups, namely extended Heisenberg groups and subgroups of the symplectic group. Interestingly, the connected shearlet group with positive dilations has an isomorphic copy in the symplectic group, while this is not true for the full shearlet group with all nonzero dilations. Indeed we prove the general result that there exist, up to adjoint action of the symplectic group, only one embedding of the extended Heisenberg algebra into the Lie algebra of the symplectic group. Having understood the various group isomorphisms it is natural to ask for the relations between coorbit spaces of isomorphic groups with equivalent representations. These connections are examined in the second part of the paper. We describe how isomorphic groups with equivalent representations lead to isomorphic coorbit spaces. In particular we apply this result to square integrable representations of the connected shearlet groups and metaplectic representations of subgroups of the symplectic group. This implies the definition of metaplectic coorbit spaces. Besides the usual full and connected shearlet groups we also deal with Toeplitz shearlet groups.     

On the meaning of mean shape: manifold stability, locus and the two sample test

Various concepts of mean shape previously unrelated in the literature are brought into relation. In particular, for non-manifolds, such as Kendall’s 3D shape space, this paper answers the question, for which means one may apply a two-sample test. The answer is positive if intrinsic or Ziezold means are used. The underlying general result of manifold stability of a mean on a shape space, the quotient due to an proper and isometric action of a Lie group on a Riemannian manifold, blends the slice theorem from differential geometry with the statistics of shape. For 3D Procrustes means, however, a counterexample is given. To further elucidate on subtleties of means, for spheres and Kendall’s shape spaces, a first-order relationship between intrinsic, residual/Procrustean and extrinsic/Ziezold means is derived stating that for high concentration the latter approximately divides the (generalized) geodesic segment between the former two by the ratio 1:3. This fact, consequences of coordinate choices for the power of tests and other details, e.g. that extrinsic Schoenberg means may increase dimension are discussed and illustrated by simulations and exemplary datasets.     

Successions in Words and Compositions

We consider words over the alphabet [k] = {1, 2, . . . , k}, k ?? 2. For a fixed nonnegative integer p, a p-succession in a word w ₁ w ₂ . . . w _n consists of two consecutive letters of the form (w _i , w _i ?+ p), i = 1, 2, . . . , n ? 1. We analyze words with respect to a given number of contained p-successions. First we find the mean and variance of the number of p-successions. We then determine the distribution of the number of p-successions in words of length n as n (and possibly k) tends to infinity; a simple instance of a phase transition (Gaussian-Poisson-degenerate) is encountered. Finally, we also investigate successions in compositions of integers.     

Soft X‐ray absorption spectroscopy and resonant inelastic X‐ray scattering spectroscopy below 100 eV: probing first‐row transition‐metal M‐edges in chemical complexes

X‐ray absorption and scattering spectroscopies involving the 3d transition‐metal K‐ and L‐edges have a long history in studying inorganic and bioinorganic molecules. However, there have been very few studies using the M‐edges, which are below 100 eV. Synchrotron‐based X‐ray sources can have higher energy resolution at M‐edges. M‐edge X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) could therefore provide complementary information to K‐ and L‐edge spectroscopies. In this study, M_2,3‐edge XAS on several Co, Ni and Cu complexes are measured and their spectral information, such as chemical shifts and covalency effects, are analyzed and discussed. In addition, M_2,3‐edge RIXS on NiO, NiF₂ and two other covalent complexes have been performed and different d–d transition patterns have been observed. Although still preliminary, this work on 3d metal complexes demonstrates the potential to use M‐edge XAS and RIXS on more complicated 3d metal complexes in the future. The potential for using high‐sensitivity and high‐resolution superconducting tunnel junction X‐ray detectors below 100 eV is also illustrated and discussed.