The effect of a heteroatom on the structure and vibrational spectra of Heteroannulated tetraphenylenes

Based on calculations by the DFT method, we have theoretically compared IR absorption and Raman spectra of tetraoxa[8]circulene (4O) and its analogs that contain sulfur (4S) and selenium (4Se) atoms. Calculations have shown that the structure of investigated molecules and observed shifts of similar vibrations in their IR and Raman spectra are interrelated. We have constructed correlation schemes of frequency shifts of normal vibrations upon passage from planar 4O circulene to its 4S and 4Se nonplanar analogs. The obtained data are of fundamental interest both from the point of view of specific selection rules and in the context of the novelty of the force field, where the conjugation of the internal and external macrocycles with heteroatoms manifests itself

Aromaticity of the doubly charged [8]circulenes

Magnetically induced current densities and current pathways have been calculated for a series of fully annelated dicationic and dianionic tetraphenylenes, which are also named [8]circulenes. The gauge including magnetically induced current (GIMIC) method has been employed for calculating the current density susceptibilities. The aromatic character and current pathways are deduced from the calculated current density susceptibilities showing that the neutral [8]circulenes have two concentric pathways with aromatic and antiaromatic character, respectively. The inner octatetraene core (the hub) is found to sustain a paratropic (antiaromatic) ring current, whereas the ring current along the outer part of the macrocycle (the rim) is diatropic (aromatic). The neutral [8]circulenes can be considered nonaromatic, because the sum of the ring-current strengths of the hub and the rim almost vanishes. The aromatic character of the doubly charged [8]circulenes is completely different: the dianionic [8]circulenes and the OC-, CH-, CH2-, SiH-, GeH-, SiH2-, and GeH2-containing dicationic species sustain net diatropic ring currents i.e., they are aromatic, whereas the O-, S-, Se-, NH-, PH- and AsH-containing dicationic [8]circulenes are strongly antiaromatic. The present study also shows that GIMIC calculations on the [8]circulenes provide more accurate information about the aromatic character than that obtained using local indices such as nuclear-independent chemical shifts (NICSs) and H-1 NMR chemical shifts.Peer reviewe

Dianthracenylazatrioxa[8]circulene: synthesis, characterization and application in OLEDs

A soluble, green-blue fluorescent, pi-extended azatrioxa[8]circulene was synthesized by oxidative condensation of a 3,6-dihydroxycarbazole and 1,4-anthraquinone by using benzofuran scaffolding. This is the first circulene to incorporate anthracene within its carbon framework. Solvent-dependent fluorescence and bright green electroluminescence accompanied by excimer emission are the key optical properties of this material. The presence of sliding pi-stacked columns in the single crystal of dianthracenylazatrioxa[8]circulene is found to cause a very high electron-hopping rate, thus making this material a promising n-type organic semiconductor with an electron mobility predicted to be around 2.26 cm(2) V-1 s(-1). The best organic light-emitting diode (OLED) device based on the dianthracenylazatrioxa[8]circulene fluorescent emitter has a brightness of around 16 000 Cd m(-2) and an external quantum efficiency of 3.3 %. Quantum dot-based OLEDs were fabricated by using dianthracenylazatrioxa[8]circulene as a host matrix material.Peer reviewe

Temperature effects in low-frequency Raman spectra of corticosteroid hormones

Experimental Raman spectra of the corticosteroid hormones corticosterone and desoxycorticosterone are recorded at different temperatures (in the range of 30–310 K) in the region of low-frequency (15–120 cm−1) vibrations using a solid-state laser at 532.1 nm. The intramolecular vibrations of both hormones are interpreted on the basis of Raman spectra calculated by the B3LYP/6-31G(d) density functional theory method. The intermolecular bonds in tetramers of hormones are studied with the help of the topological theory of Bader using data of X-ray structural analysis for crystalline samples of hormones. The total energy of intermolecular interactions in the tetramer of desoxycorticosterone (−49.1 kJ/mol) is higher than in the tetramer of corticosterone (−36.9 kJ/mol). A strong intramolecular hydrogen bond O21-H⋯O=C20 with an energy of −42.4 kJ/mol was revealed in the corticosterone molecule, which is absent in the desoxycorticosterone molecule. This fact makes the Raman spectra of both hormones somewhat different. It is shown that the low-frequency lines in the Raman spectra are associated with skeletal vibrations of molecules and bending vibrations of the substituent at the C17 atom. The calculated Raman spectrum of the desoxycorticosterone dimer allows one to explain the splitting and shift of some lines and to interpret new strong lines observed in the spectra at low temperatures, which are caused by the intermolecular interaction and mixing of normal vibrations in a crystal cell. On the whole the calculated frequencies are in a good agreement with the experimental results

New records of Holocene polar bear and walrus (Carnivora) in the Russian Arctic

This article discusses recent finds of Holocene polar bear and walrus from the northern regions of Russia. The ulna of a polar bear was found on Vaygach Island and radiocarbon dated to 1,971 +/- 25 BP (OxA-23631). This calibrates to 430-540 AD, taking into account the marine reservoir effect. The size of the bone is similar to that of a recent Ursus maritimus. The locality of the fossil bone is within the modern species range, which developed about two millennia ago. In 2014 a walrus tusk was found on the coast of New Siberia Island and is radiocarbon dated to 5,065 +/- 35 BP (GrA-62452). This calibrates to 3,510-3,370 BC, taking into account the marine reservoir effect. Its size and morphology are identical to that of an adult male of the subspecies Odobenus rosmarus laptevi. This subspecies populates the eastern parts of the Kara Sea, the entire Laptev Sea and the western parts of the East Siberian Sea. This new discovery could mean that populations of O. rosmarus laptevi inhabited the waters near the New Siberian Islands during the Middle Holocene, and that the present-day coastline of the Siberian Arctic Islands was already formed at that time

The blue vibronically resolved electroluminescence of azatrioxa[8]circulene

Organic Light Emitting Dioides (OLED)devices were fabricated with blue emission based on azatrioxa[8]circulene and 4,4-N,N'-Dicarbazolyl-1,1'-biphenyl (CBP) with maximum brightness of 840 kd/m(2) at 12 V and the starting voltage of 3.5 V. The vibronic emission spectrum was analyzed by the promotive modes calculation method. The electroluminescence of fabricated OLED device is caused by the 0-0 electronic transition and single excitations of 1473 cm(-1) and 1673 cm(-1) modes and combinations thereof.Peer reviewe

On recurrence and ergodicity for geodesic flows on noncompact periodic polygonal surfaces

We study the recurrence and ergodicity for the billiard on noncompact polygonal surfaces with a free, cocompact action of $\Z$ or $\Z^2$. In the $\Z$-periodic case, we establish criteria for recurrence. In the more difficult $\Z^2$-periodic case, we establish some general results. For a particular family of $\Z^2$-periodic polygonal surfaces, known in the physics literature as the wind-tree model, assuming certain restrictions of geometric nature, we obtain the ergodic decomposition of directional billiard dynamics for a dense, countable set of directions. This is a consequence of our results on the ergodicity of \ZZ-valued cocycles over irrational rotations.Comment: 48 pages, 12 figure

On the partial connection between random matrices and interacting particle systems

In the last decade there has been increasing interest in the fields of random matrices, interacting particle systems, stochastic growth models, and the connections between these areas. For instance, several objects appearing in the limit of large matrices arise also in the long time limit for interacting particles and growth models. Examples of these are the famous Tracy-Widom distribution functions and the Airy_2 process. The link is however sometimes fragile. For example, the connection between the eigenvalues in the Gaussian Orthogonal Ensembles (GOE) and growth on a flat substrate is restricted to one-point distribution, and the connection breaks down if we consider the joint distributions. In this paper we first discuss known relations between random matrices and the asymmetric exclusion process (and a 2+1 dimensional extension). Then, we show that the correlation functions of the eigenvalues of the matrix minors for beta=2 Dyson's Brownian motion have, when restricted to increasing times and decreasing matrix dimensions, the same correlation kernel as in the 2+1 dimensional interacting particle system under diffusion scaling limit. Finally, we analyze the analogous question for a diffusion on (complex) sample covariance matrices.Comment: 31 pages, LaTeX; Added a section concerning the Markov property on space-like path

Evolutionary History of Saber-Toothed Cats Based on Ancient Mitogenomics

Saber-toothed cats (Machairodontinae) are among the most widely recognized representatives of the now largely extinct Pleistocene megafauna. However, many aspects of their ecology, evolution, and extinction remain uncertain. Although ancient-DNA studies have led to huge advances in our knowledge of these aspects of many other megafauna species (e.g., mammoths and cave bears), relatively few ancient-DNA studies have focused on saber-toothed cats [1–3], and they have been restricted to short fragments of mitochondrial DNA. Here we investigate the evolutionary history of two lineages of saber-toothed cats (Smilodon and Homotherium) in relation to living carnivores and find that the Machairodontinae form a well-supported clade that is distinct from all living felids. We present partial mitochondrial genomes from one S. populator sample and three Homotherium sp. samples, including the only Late Pleistocene Homotherium sample from Eurasia [4]. We confirm the identification of the unique Late Pleistocene European fossil through ancient-DNA analyses, thus strengthening the evidence that Homotherium occurred in Europe over 200,000 years later than previously believed. This in turn forces a re-evaluation of its demography and extinction dynamics. Within the Machairodontinae, we find a deep divergence between Smilodon and Homotherium (∼18 million years) but limited diversity between the American and European Homotherium specimens. The genetic data support the hypothesis that all Late Pleistocene (or post-Villafrancian) Homotherium should be considered a single species, H. latidens, which was previously proposed based on morphological data [5, 6]. Paijmans et al. present ancient DNA from some of the most recognized extinct Pleistocene megafauna: the saber-toothed cats. The results elucidate the evolutionary history of these iconic carnivores and provide genetic evidence that saber-toothed cats existed in Europe over 200,000 years later than previously believed.This project received funding from the European Research Council (consolidator grant GeneFlow no. 310763 to M.H.), European Union’s Seventh Framework Programme for research, technological development, and demonstration (grant no. FP7-PEOPLE-2011-IEF-298820 to R.B.), and Lundbeck Foundation (grant no. R52-A5062 to M.L.Z.-M.)