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Confined environments can be used to alter the selectivity of a reaction by influencing the organization of the reactants, altering the mobility of trapped molecules, facilitating one reaction pathway or selectively stabilizing the products. This manuscript utilizes a series of potentially photoreactive guests to interrogate the utility of the one-dimensional nanochannels of a porous host to absorb and facilitate the reaction of encapsulated guests. The host is a columnar self-assembled phenylethynylene bis-urea macrocycle, which absorbs guests, including coumarin, 6-methyl coumarin, 7-methyl coumarin, 7-methoxy coumarin, acenaphthylene, cis-stilbene, trans-stilbene, and trans-ß-methylstyrene to afford crystalline inclusion complexes. We examine the structure of the host:guest complexes using powder X-ray diffraction, which suggests that they are well-ordered highly crystalline materials. Investigations using solid-state cross-polarized magic angle spinning (13)C{(1)H}CP-MAS NMR spectroscopy indicate that the guests are mobile relative to the host. Upon UV-irradiation, we observed selective photodimerization reactions for coumarin, 6-methyl coumarin, 7-methyl coumarin, and acenaphthylene, while the other substrates were unreactive even under prolonged UV-irradiation. Grand Canonical Monte Carlo simulations suggest that the reactive guests were close paired and preorganized in configurations that facilitate the photodimerization with high selectivity while the unreactive guests did not exhibit similar close pairing. A greater understanding of the factors that control diffusion and reaction in confinement could lead to the development of better catalysts.
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Three quaternary mercury bismuth chalcohalides, Hg3Q2Bi2Cl8 (Q = S, Se, Te), are reported along with their syntheses, crystal structures, electronic band structures, and optical properties. The compounds are structurally similar with a layer comprised of a hole perforated sheet network of [Hg3Q2](2+) (Q = S and Te) that forms by fused cyclohexane, chairlike Hg6Q6 rings. The cationic charge in the network is balanced by edge-sharing monocapped trigonal-prismatic anions of [Bi2Cl8](2-) that form a two-dimensional network located between layers. Compound 1, Hg3S2Bi2Cl8, crystallizes in the monoclinic space group C12/m1 with a = 12.9381(9) Å, b = 7.3828(6) Å, c = 9.2606(6) Å, and ß = 116.641(5)°. Compound 2, Hg3Te2Bi2Cl8, crystallizes in the monoclinic space group C12/c1 with a = 17.483(4) Å, b = 7.684(2) Å, c = 13.415(3) Å, and ß = 104.72(3)°. The crystals of the Hg3Se2Bi2Cl8 analogue exhibit complex modulations and structural disorder, which complicated its structural refinement. Compounds 1 and 2 melt incongruently and show band gaps of 3.26 and 2.80 eV, respectively, which are in a good agreement with those from band-structure density functional theory calculations.
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We investigated an antimony chalcohalide compound, SbSeI, as a potential semiconductor material for X-ray and γ-ray detection. SbSeI has a wide band gap of 1.70 eV with a density of 5.80 g/cm(3), and it crystallizes in the orthorhombic Pnma space group with a one-dimensional chain structure comprised of infinite zigzag chains of dimers [Sb2Se4I8]n running along the crystallographic b axis. In this study, we investigate conditions for vertical Bridgman crystal growth using combinations of the peak temperature and temperature gradients as well as translation rate set in a three-zone furnace. SbSeI samples grown at 495 °C peak temperature and 19 °C/cm temperature gradient with 2.5 mm/h translation rate produced a single phase of columnar needlelike crystals aligned along the translational direction of the growth. The ingot sample exhibited an n-type semiconductor with resistivity of â¼10(8) Ω·cm. Photoconductivity measurements on these specimens allowed us to determine mobility-lifetime (µτ) products for electron and hole carriers that were found to be of similar order of magnitude (â¼10(-4) cm(2)/V). Further, the SbSeI ingot with well-aligned, one-dimensional columnar needlelike crystals shows an appreciable response of Ag Kα X-ray.
Assuntos
Antimônio/química , Calcogênios/química , Iodetos/química , Semicondutores , Microscopia Eletrônica de Varredura , Modelos Moleculares , Processos Fotoquímicos , RadioatividadeRESUMO
The new compounds TlHg6Q4Br5 (Q = S, Se) are reported along with their syntheses, crystal structures, and thermal and optical properties, as well as electronic band structure calculations. Both compounds crystallize in the tetragonal I4/m space group with a = 14.145(1) Å, c = 8.803(1) Å, and dcalc = 7.299 g/cm(3) for TlHg6S4Br5 (compound 1) and a = 14.518(2) Å, c = 8.782(1) Å, and dcalc = 7.619 g/cm(3) for TlHg6Se4Br5 (compound 2). They consist of cuboid Hg12Q8 building units interconnected by trigonal pyramids of BrHg3, forming a three-dimensional structure. The interstitial spaces are filled with thallium and bromide ions. Compounds 1 and 2 melt incongruently and show band gaps of 3.03 and 2.80 eV, respectively, which agree well with the calculated ones. First-principles electronic structure calculations at the density functional theory level reveal that both compounds have indirect band gaps, but there also exist direct transitions at energies similar to the indirect gaps.
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There is much interest in designing molecular sized containers that influence and facilitate chemical reactions within their nanocavities. On top of the advantages of improved yield and selectivity, the studies of reactions in confinement also give important clues that extend our basic understanding of chemical processes. We report here, the synthesis and self-assembly of an expanded bis-urea macrocycle to give crystals with columnar channels. Constructed from two C-shaped phenylethynylene units and two urea groups, the macrocycle affords a large pore with a diameter of â¼9 Å. Despite its increased size, the macrocycles assemble into columns with high fidelity to afford porous crystals. The porosity and accessibility of these channels have been demonstrated by gas adsorption studies and by the uptake of coumarin to afford solid inclusion complexes. Upon UV-irradiation, these inclusion complexes facilitate the conversion of coumarin to its anti-head-to-head (HH) photodimer with high selectivity. This is contrary to what is observed upon the solid-state irradiation of coumarin, which affords photodimers with low selectivity and conversion.
Assuntos
Alcinos/química , Cumarínicos/química , Compostos Macrocíclicos/química , Fenetilaminas/química , Ureia/química , Dimerização , Processos FotoquímicosRESUMO
The ordered double-perovskites Sr(2)MOsO(6) (M = Cu, Ni) consisting of 3d and 5d transition-metal magnetic ions (M(2+) and Os(6+), respectively) are magnetic insulators; the magnetic susceptibilities of Sr(2)CuOsO(6) and Sr(2)NiOsO(6) obey the Curie-Weiss law with dominant antiferromagnetic and ferromagnetic interactions, respectively, and the zero-field-cooled and field-cooled susceptibility curves of both compounds diverge below â¼20 K. In contrast, the available density functional studies predicted both Sr(2)CuOsO(6) and Sr(2)NiOsO(6) to be metals. We resolved this discrepancy on the basis of systematic density functional calculations. The magnetic insulating states of Sr(2)MOsO(6) are found only when a substantially large on-site repulsion is employed for the Os atom, although it is a 5d element. The cause for the divergence between the zero-field-cooled and field-cooled susceptibility curves in both compounds and the reason for the difference in their dominant magnetic interactions were investigated by examining their spin exchange interactions.
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Reported is a macrocyclic diacetylene that assembled into columns to afford porous crystals. Heating this assembly initiated a topochemical polymerization of the preorganized diacetylene units to give covalent conjugated polydiacetylenes. These stable conjugated materials maintained permanent porosity as evidenced by their type I gas adsorption isotherms with CO(2) (g). Such conjugated polymeric nanotubes could possess unusual properties for sensing and electronics.
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New two-dimensional (2D) bismuth and three-dimensional (3D) lead based coordination polymers containing pyridine-2,5-dicarboxylate ligands (H(2)pydc) have been synthesized hydrothermally and characterized by single crystal X-ray diffraction. Bi(3)(µ(3)-O)(2)(pydc)(2)(Hpydc)(H(2)O)(2) (1), which crystallizes in the space group P1Ì (a = 8.7256(5) Å, b = 11.1217(7) Å, c = 14.0933(9) Å, α = 85.239(1)°, ß = 98.582(1)°, γ = 71.106(1)°), has a 3D structure that contains Bi(6)O(4) clusters that connect into 2D sheets via linking ligands. The sheets form a 3D supramolecular structure via hydrogen bonding along the z-axis. Pb(pydc)(H(2)O) (2), which crystallizes in the space group P2(1)/c (a = 10.8343(14) Å, b = 11.2099(15) Å, c = 6.6573(9) Å, ß = 90.697(2)°), contains 1D chains of corner-sharing distorted face capped trigonal prisms that are connected into a 3D framework via the pydc ligand. In addition, the ligands are hydrogen bonded to each other. Both 1 and 2 are single component "white" light emitting phosphors and are shown to exhibit "white" luminescence that covers a much wider spectral range than is observed for the as received H(2)pydc ligand.
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A new Kagomé lattice topology assembled from ML(4) metal-organic polyhedra prepared using bismuth nitrate and pyridine-2,5-dicarboxylate has been obtained via a solvo-thermal reaction. Bi(pydc)(2)·(H(3)O(+))(H(2)O)(0.83) is, to the best of our knowledge, the first example of a bismuth-based coordination polymer to form with a Kagomé topology. Its structure and photoluminescence properties are reported.
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Pyridine macrocycles with no cavities assembled into close packed columns yet absorbed guests including hydrogen, carbon dioxide, and iodine.