Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

N-Methyl-N-nitroso-p-toluene-sulfon-amide.

The crystal structure of the title compound, C8H10N2O3S, displays predominant C-H⋯O hydrogen-bonding and π-π stacking inter-actions. The hydrogen bonds are between the O atoms of the sulfonyl group and H atoms on methyl groups. The π-π stacking inter-actions occur between adjacent aromatic rings, with a centroid-centroid distance of 3.868 (11) Å. These inter-actions lead to the formation of chains parallel to (101).

N-[2-(Pyridin-2-yl)ethyl]-derivatives of methane-, benzene- and toluenesulfonamide: prospective ligands for metal coordination.

The molecular and supramolecular structures are reported of N-[2-(pyridin-2-yl)ethyl]methanesulfonamide, C8H12N2O2S, (I), N-[2-(pyridin-2-yl)ethyl]benzenesulfonamide, C13H14N2O2S, (II), and N-[2-(pyridin-2-yl)ethyl]toluenesulfonamide, C14H16N2O2S, (III). Although (II) and (III) are almost structurally identical, the N(amide)-C(ethyl)-C(ethyl)-C(pyridinyl) torsion angles for (I) and (II) are more closely comparable, with magnitudes of 175.37 (15)° for (I) and 169.04 (19)° for (II). This angle decreases dramatically with an additional methyl group in the para position of the sulfonamide substituent, resulting in a value of 62.9 (2)° for (III). In each of the three compounds there is an N-H...N hydrogen bond between the sulfonamide of one molecule and the pyridine N atom of a neighbor. Compound (I) forms hydrogen-bonded dimers, (II) uses its hydrogen bonding to connect supramolecular layers, and the hydrogen bonding of (III) connects linear chains to form layers. For arene-substituted (II) and (III), the different conformations afforded by the variable dihedral angles promote intermolecular π-π stacking in the benzene-substituted structure (II), but distorted intramolecular T-shaped π-stacking in the toluene-substituted structure (III), with a centroid-to-centroid distance of 4.9296 (10) Å.

1,6-Di-bromo-naphthalen-2-ol methanol monosolvate.

The naphthol-containing mol-ecule of the title compound, C10H6Br2O·CH3OH, crystallized as a methanol monosolvate and is planar to within 0.069 (1) Šfor all non-H atoms. In the crystal, mol-ecules are linked by two pairs of O-H⋯O hydrogen bonds, involving the methanol mol-ecule, forming dimer-like arrangements. The crystal structure is further stabilized by π-π stacking [centroid-centroid distance = 3.676 (2) Å] and Br⋯Br inter-actions [3.480 (4) and 3.786 (1) Å], forming a three-dimensional structure.

1,3-Bis(chloro-meth-yl)benzene.

The title compound, C8H8Cl2, used in the synthesis of many pharmaceutical inter-mediates, forms a three-dimensional network through chlorine-chlorine inter-actions in the solid-state that measure 3.513 (1) and 3.768 (3) Å.

(1H-Imidazol-4-yl)methanol.

The title compound, C4H6N2O, displays two predominant hydrogen-bonding inter-actions in the crystal structure. The first is between the unprotonated imidazole N atom of one mol-ecule and the hy-droxy H atom of an adjacent mol-ecule. The second is between the hy-droxy O atom of one mol-ecule and the imidazole N-H group of a corresponding mol-ecule. These inter-actions lead to the formation of a two-dimnensional network parallel to (10-1). C-H⋯O inter-actions also occur.

Benzo[1,2-b:4,5-b']dithio-phene-4,8-dione.

The title mol-ecule, C(10)H(4)O(2)S(2), is situated on a crystallographic center of inversion. In the crystal, weak hydrogen bonding contributes to the packing of the mol-ecules.

High T(c) electron doped Ca10(Pt3As8)(Fe2As2)5 and Ca10(Pt4As8)(Fe2As2)5 superconductors with skutterudite intermediary layers.

It has been argued that the very high transition temperatures of the highest T(c) cuprate superconductors are facilitated by enhanced CuO(2) plane coupling through heavy metal oxide intermediary layers. Whether enhanced coupling through intermediary layers can also influence T(c) in the new high T(c) iron arsenide superconductors has never been tested due the lack of appropriate systems for study. Here we report the crystal structures and properties of two iron arsenide superconductors, Ca(10)(Pt(3)As(8))(Fe(2)As(2))(5) (the "10-3-8 phase") and Ca(10)(Pt(4)As(8))(Fe(2)As(2))(5) (the "10-4-8 phase"). Based on -Ca-(Pt(n)As(8))-Ca-Fe(2)As(2)- layer stacking, these are very similar compounds for which the most important differences lie in the structural and electronic characteristics of the intermediary platinum arsenide layers. Electron doping through partial substitution of Pt for Fe in the FeAs layers leads to T(c) of 11 K in the 10-3-8 phase and 26 K in the 10-4-8 phase. The often-cited empirical rule in the arsenide superconductor literature relating T(c) to As-Fe-As bond angles does not explain the observed differences in T(c) of the two phases; rather, comparison suggests the presence of stronger FeAs interlayer coupling in the 10-4-8 phase arising from the two-channel interlayer interactions and the metallic nature of its intermediary Pt(4)As(8) layer. The interlayer coupling is thus revealed as important in enhancing T(c) in the iron pnictide superconductors.

Cs6Nb4Se22 and K12Nb6Se35.3: two new compounds containing the M4Q22 building block.

The title compounds, namely hexacaesium tetraniobium docosaselenide and dodecapotassium hexaniobium pentatriacontaselenide, were formed from their respective alkali chalcogenide reactive flux and niobium metal. Both compounds fall into the larger family of solid-state compounds that contain the M(2)Q(11) building block (M = Nb, Ta; Q = Se, S), where the metal chalcogenide forms dimers of face-shared pentagonal bipyramids. Cs(6)Nb(4)Se(22) contains two Nb(2)Se(11) building blocks linked by an Se-Se bond to form isolated Nb(4)Se(22) tetrameric building blocks surrounded by caesium ions. K(12)Nb(6)Se(35.3) contains similar Nb(4)Se(22) tetramers that are linked by an Se-Se-Se unit to an Nb(2)Se(11) dimer to form one-dimensional anionic chains surrounded by potassium ions. Further crystallographic studies of K(12)Nb(6)Se(35.3) demonstrate a new M(2)Se(12) building block because of disorder between an Se(2-) site (85%) and an (Se-Se)(2-) unit (15%). The subtle differences between the structures are discussed.

1-Methyl-4H-3,1-benzoxazine-2,4(1H)dione.

In its crystal structure, the title compound, C(9)H(7)NO(3), forms π-stacked dimers, with a centroid-centroid distance of 3.475 (5) Šbetween the benzenoid and the 2,4 dicarbonyl oxazine rings. These dimers then form staircase-like linear chains through further π-stacking between the benzenoid rings [centroid-centroid distance of 3.761 (2) Å]. The methyl-H atoms are disordered due to rotation about the C-N bond and were modeled with equal occupancy.

Directed-sorting method for synthesis of bead-based combinatorial libraries of heterogeneous catalysts.

The synthesis and analysis of inorganic material combinatorial libraries by a directed-sorting, split-pool bead method was demonstrated. Directed-sorting, split-pool, metal-loaded libraries were synthesized by adsorbing metal salts (H2PtCl6, SnCl2, CuCl2, and NiCl2) and metal standards (Pt, Cu, Ni in HCl) onto 2-mg porous gamma-alumina beads in 96- or 384-well plates. A matrix algorithm for the synthesis of bead libraries treated each bead as a member of a row or column of a given matrix. Computer simulations and manual tracking of the sorting process were used to assess library diversity. The bead compositions were analyzed by energy-dispersive X-ray spectroscopy, X-ray fluorescence spectroscopy, electron probe microanalysis, inductively coupled plasma atomic emission spectroscopy, and inductively coupled plasma mass spectroscopy. The metal-loaded beads were analyzed by laser-activated membrane introduction mass spectroscopy (LAMIMS) for catalytic activity using methylcyclohexane dehydrogenation to toluene as a probe reaction. The catalytic activity of individual beads that showed minimal (approximately 20% of that of Pt on alumina) to high conversion could be determined semiquantitatively by LAMIMS. This method, therefore, provides an alternative to screening using microreactors for reactors that employ catalysts in the form of beads. The directed-sorting method offers the potential for synthesis of focused libraries of inorganic materials through relatively simple benchtop split-pool chemistry.

Three new phases in the K/Cu/Th/S system: KCuThS3, K2Cu2ThS4, and K3Cu3Th2S7.

Synthetic exploration of K/Cu/Th/S quaternary phase space has yielded three new compounds: KCuThS3 (I), K2Cu2ThS4 (II), and K3Cu3Th2S7 (III). All three phases are semiconductors with optical band gaps of 2.95, 2.17, and 2.49 eV(I-III). Compound I crystallizes in the orthorhombic space group Cmcm with a = 4.076(1) A, b = 13.864(4) A, and c = 10.541(3) A. Compound II crystallizes in the monoclinic space group C2/m with a = 14.522(1) A, b = 4.026(3) A, and c = 7.566(6) A; beta = 109.949(1) degrees . Compound III crystallizes in orthorhombic space group Pbcn with a = 4.051(2) A, b = 14.023(8) A, and c = 24.633(13) A. The compounds are all layered materials, with each layer composed of threads of edge-sharing ThS6 octahedra bridged by CuS4 tetrahedral threads of varying dimension. The layers are separated by well-ordered potassium ions. The relatively wide range of optical band gaps is attributed to the extent of the CuS4 motifs. As the dimension of the CuS4 chains increases, band gaps decrease in the series. All materials were characterized by single-crystal X-ray diffraction, microprobe chemical analysis, and diffuse reflectance spectroscopy (NIR-UV).

Synthesis and characterization of two quaternary thorium chalcophosphates: Cs4Th2P6S18 and Rb7Th2P6Se21.

Two new thorium chalcophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction, diffuse reflectance, and Raman spectroscopy: Cs4Th2P6S18 (I); Rb7Th2P6Se21 (II). Compound I crystallizes as colorless blocks in the triclinic space group P1 (No. 2) with a = 12.303(4) A, b = 12.471(4) A, c = 12.541(4) A, alpha = 114.607(8) degrees, beta = 102.547(6) degrees, gamma = 99.889(7) degrees, and Z = 2. The structure consists of (Th2P6S18)(4-) layers separated by layers of cesium cations and only contains the (P2S6)(4-) building block. Compound II crystallizes as red blocks in the triclinic space group P1 (No. 2) with a = 11.531(3) A, b = 12.359(4) A, c = 16.161(5) A, alpha = 87.289(6) degrees, beta = 75.903(6) degrees, gamma = 88.041(6) degrees, and Z = 2. The structure consists of linear chains of (Th2P6Se21)(7-) separated by rubidium cations. Compound II contains both the (PSe4)(3-) and (P2Se6)(4-) building blocks. Both structures may be derived from two known rare earth structures where a rare earth site is replaced by an alkali or actinide metal to form these novel structures. Optical band gap measurements show that compound I has a band gap of 2.8 eV and compound II has a band gap of 2.0 eV. Solid-state Raman spectroscopy of compound I shows the vibrations expected for the (P2S6)(4-) unit. Raman spectroscopy of compound II shows the vibrations expected for both (PSe4)(3-) and (P2Se6)(4-) units. Our work shows the remarkable diversity of the actinide chalcophosphate system and demonstrates the phase space is still ripe to discover new structures.

Synthesis and characterization of AU2Se6 (A = K, Cs).

Two new ternary uranium selenides, AU(2)Se(6) (A = K, Cs), were prepared using the reactive flux method. Single crystal X-ray diffraction was performed on single crystals. The compounds crystallize in the orthorhombic Immm space group, Z = 2. CsU(2)Se(6) has cell parameters of a = 4.046(2) A, b = 5.559(3) A, and c = 24.237(12) A. KU(2)Se(6) has cell parameters of a = 4.058(3) A, b = 5.556(4) A, and c = 21.710(17) A. The compounds are isostructural to the previously reported KTh(2)Se(6). The two-dimensional layered structure is related to ZrSe(3) with the alkali metals residing in the interlayer space. The oxidation states of uranium and selenium were evaluated using X-ray photoelectron spectroscopy (XPS). Uranium was found to be tetravalent, while selenium was found to be in two oxidation states, one of which is -2. The other oxidation state is similar to that found in a polyselenide network. While this structure is known, our work examines how the structure changes through the transactinide series.

Split-pool method for synthesis of solid-state material combinatorial libraries.

The synthesis and analysis of inorganic material combinatorial libraries by the split-pool bead method were demonstrated at the proof-of-concept level. Millimeter-size spherical beads of porous gamma-alumina, a commonly used support material for heterogeneous catalysts, were modified with Al(13)O(4)(OH)(24)(H(2)O)(12)(7+) cations in order to promote irreversible adsorption of the anionic fluorescent dyes Cascade Blue, Lucifer Yellow, and Sulforhodamine 101. The compositions of individual beads were easily determined through three split-pool cycles using a conventional fluorescence plate reader. Small split-pool material libraries were made by adsorbing noble metal salts (H(2)PtCl(6), H(2)IrCl(6), and RhCl(3)) into the beads. Analysis of these beads by micro-X-ray fluorescence showed that quantitative adsorption of metal salts without cross-contamination of beads could be achieved at levels (0.3 wt % metal loading) relevant to heterogeneous catalysis. The method offers the potential for synthesis of rather large libraries of inorganic materials through relatively simple benchtop split-pool chemistry.