7 research outputs found

    Zwitterionic iodonium species afford halogen bond-based porous organic frameworks

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    Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified in two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The channels are filled with disordered water molecules which can be reversibly removed on heating. Consistent with the remarkable strength and directionality of the halogen bonds (XBs) driving the crystal packing formation, the porous structure is stable and fully preserved on almost quantitative removal and readsorption of water. The porous systems described here are the first reported cases of one-component 3D organic frameworks whose assembly is driven by XB only (XOFs). These systems are a proof of concept for the ability of zwitterionic aryliodonium tectons in affording robust one-component 3D XOFs. The high directionality and strength of the XBs formed by these zwitterions and the geometrical constraints resulting from the tendency of their hypervalent iodine atoms to act as bidentate XB donors might be key factors in determining this ability

    Supramolecular Assembly of Metal Complexes by (Aryl)I⋯dz2[PtII] Halogen Bond

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    The theoretical data for the half‐lantern complexes [Pt(C^N)(Ό‐S^N)] 2 ( 1 – 3 ; ĐĄ^N is cyclometalated 2‐Ph‐benzothiazole; S^N is 2‐SH‐pyridine 1 , 2‐SH‐benzoxazole 2 , 2‐SH‐tetrafluorobenzothiazole 3 ) indicate that the Pt···Pt orbital interaction leads to an increment of the nucleophilicity of the outer d z 2 ‐orbitals to provide assembly with electrophilic species. 1 – 3 were co‐crystallized with bifunctional halogen bond (XB) donors to give adducts ( 1 – 3 ) 2 ∙(1,4‐diiodotetrafluorobenzene) and infinite polymeric [ 1 ·1,1’‐diiodoperfluorodiphenyl] n . X‐ray crystallography revealed that the supramolecular assembly is achieved via (Aryl)I∙∙∙ d z 2 [Pt II ] XB between iodine σ‐holes and lone pairs of the positively charged (Pt II ) 2 centers, acting as nucleophilic sites. The polymer includes a curved linear chain ···Pt 2 ···I(arene F )I···Pt 2 ··· involving XB between iodines of the perfluoroarene linkers and (Pt II ) 2 moieties. The 195 Pt NMR, UV‐vis, and CV studies indicate that XB is preserved in CH(D) 2 Cl 2 solutions.peerReviewe

    The biogeography of Elaphe sauromates (Pallas, 1814), with a description of a new rat snake species

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    Background The rat snake genus Elaphe once comprised several dozens of species distributed in temperate through tropical zones of the New and Old World. Based on molecular-genetic analyses in early 2000s, the genus was split into several separate genera, leaving only 15 Palearctic and Oriental species as its members. One of the three species also occurring in Europe is Elaphe sauromates, a robust snake from the Balkans, Anatolia, Caucasus, Ponto-Caspian steppes, and Levant that has been suspected to be composed of two or more genetically diverse populations. Here, we studied the genetic structure and morphological variation of E. sauromates, aiming to better understand its inter-population relationships and biogeography, and subsequently revise its taxonomy. Methods We reconstructed the phylogeography and analyzed the genetic structure of E. sauromates populations originating from most of its geographic range using both mitochondrial (COI, ND4) and nuclear (C-MOS, MC1R, PRLR, RAG1) DNA gene fragments. We employed Maximum likelihood and Bayesian inference methods for the phylogenetic tree reconstructions, supplemented with species delimitation methods, analysis of haplotype networks, and calculation of uncorrected p-distances. Morphological variation in 15 metric and 18 meristic characters was studied using parametric univariate tests as well as multivariate general linearized models. In total, we analyzed sequences originating from 63 specimens and morphological data from 95 specimens of E. sauromates sensu lato. Results The molecular phylogeny identified two clearly divergent sister lineages within E. sauromates, with both forming a lineage sister to E. quatuorlineata. The genetic distance between them (5.80–8.24% in mtDNA) is similar to the distances among several other species of the genus Elaphe. Both lineages are also moderately morphologically differentiated and, while none of the characters are exclusively diagnostic, their combination can be used for confident lineage identification. Here, following the criteria of genetic and evolutionary species concepts, we describe the lineage from eastern Anatolia and parts of the Lesser and Great Caucasus as a new species E. urartica sp. nov. Discussion Elaphe urartica sp. nov. represents a cryptic species whose ancestors presumably diverged from their common ancestor with E. sauromates around the Miocene-Pliocene boundary. The intraspecific genetic structure indicates that the recent diversity of both species has been predominantly shaped by Pleistocene climatic oscillations, with glacial refugia mainly located in the Balkans, Crimea, and/or Anatolia in E. sauromates and Anatolia and/or the Caucasus in E. urartica sp. nov

    Morphological and genetic differentiation in the anguid lizard Pseudopus apodus supports the existence of an endemic subspecies in the Levant

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    The Levant represents one of the most important reptile diversity hotspots and centers of endemism in the Western Palearctic. The region harbored numerous taxa in glacial refugia during the Pleistocene climatic oscillations. Due to the hostile arid conditions in the warmer periods they were not always able to spread or come into contact with populations from more distant regions. One large and conspicuous member of the Levantine herpetofauna is the legless anguid lizard Pseudopus apodus. This species is distributed from the Balkans to Central Asia with a portion of its range running along the eastern Mediterranean coast. Mitochondrial and nuclear DNA sequences, microsatellite genotypes, and morphology show that populations in this region differ from the two named subspecies and presumably had a long independent evolutionary history during the Quaternary. Here we describe the Levantine population as a new subspecies and present biogeographic scenarios for its origin and diversification. The new subspecies is genetically highly diverse, and it forms a sister lineage to Pseudopus from the remaining parts of the range according to mtDNA. It is the largest-bodied of the three subspecies, but occupies the smallest range
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