Crystal structure and Hirshfeld surface analysis of (nitrato-κ ,')(1,4,7,10-tetra-aza-cyclo-dodecane-κ )nickel(II) nitrate.

The crystal structure of the title compound, [Ni(CHN)(NO)]NO, at room temperature, has monoclinic (2/) symmetry. The structure displays inter-molecular hydrogen bonding. The nickel displays a distorted bipyramidal geometry with the symmetric bidentate bonded nitrate occupying an equatorial site.

Structural Integrities of Symmetric and Unsymmetric -Bis-pyridyl Ethylene Powders Exposed to Gamma Radiation: Packing and Electronic Considerations Assisted by Electron Diffraction.

Radiation detection (dosimetry) most commonly uses scintillating materials in a wide array of fields, ranging from energy to medicine. Scintillators must be able to not only fluoresce owing to the presence of a suitable chromophore but also withstand damage from radiation over prolonged periods of time. While it is inevitable that radiation will cause damage to the physical and chemical properties of materials, there is limited understanding of features within solid-state scintillators that afford increased structural integrity upon exposure to gamma (γ) radiation.

Confinement and Separation of Benzene from an Azeotropic Mixture Using a Chlorinated B←N Adduct.

Separations of azeotropic mixtures are typically carried out using energy-demanding processes (e.g., distillation).

Crystal structure of tricarbon-yl[η-6--(tri-phenyl-phosphino)cyclo-hepta-2,4-dien-1-one]iron(0) tetra-fluoro-borate.

The mol-ecular structure of tricarbon-yl[η-6--(tri-phenyl-phosphino)cyclo-hepta-2,4-dien-1-one]iron(0) tetra-fluoro-borate di-chloro-methane hemisolvate, [Fe(CHO)(CO)]BF·0.5CHCl, as determined by single-crystal X-ray diffraction is reported. The two independent tricarbon-yl[η-6--(tri-phenyl-phosphino)cyclo-hepta-2,4-dien-1-one] iron(0) cations and their corresponding anions form dimers, which constitute the asymmetric unit of the structure parallel to the (100) plane.

Silver 2,4'-Bipyridine Coordination Polymer for the High-Capacity Trapping of Perrhenate, A Pertechnetate Surrogate.

Pertechnetate, the most stable form of the radionuclide Tc in aerobic aqueous systems, is a hazardous anion present in nuclear waste. Its high mobility in water makes the remediation of the anion challenging. In the past decade, significant effort has been placed into finding materials capable of adsorbing this species.

A molecular T-pentomino for separating BTEX hydrocarbons.

Methods to separate molecules (e.g., petrochemicals) are exceedingly important industrially.

Rational Design and Reticulation of Infinite qbe Rod Secondary Building Units into Metal-Organic Frameworks through a Global Desymmetrization Approach for Inverse C H /C H Separation.

The development of reticular chemistry has enabled the construction of a large array of metal-organic frameworks (MOFs) with diverse net topologies and functions. However, dominating this class of materials are those built from discrete/finite secondary building units (SBUs), yet the designed synthesis of frameworks involving infinite rod-shaped SBUs remain underdeveloped. Here, by virtue of a global linker desymmetrization approach, we successfully targeted a novel Cu-MOF (Cu-ASY) incorporating infinite Cu-carboxylate rod SBUs with its structure determined by micro electron diffraction (MicroED) crystallography.

Modulator-Dependent Dynamics Synergistically Enabled Record SO Uptake in Zr(IV) Metal-Organic Frameworks Based on Pyrene-Cored Molecular Quadripod Ligand.

Developing innovative porous solid sorbents for the capture and storage of toxic SO is crucial for energy-efficient transportation and subsequent processing. Nonetheless, the quest for high-performance SO sorbents, characterized by exceptional uptake capacity, minimal regeneration energy requirements, and outstanding recyclability under ambient conditions, remains a significant challenge. In this study, we present the design of a unique tertiary amine-embedded, pyrene-based quadripod-shaped ligand.

Co-crystal sustained by π-type halogen-bonding inter-actions between 1,4-di-iodo-perchloro-benzene and naphthalene.

The formation and crystal structure of a co-crystal based upon 1,4-di-iodo-perchloro-benzene (CICl) as the halogen-bond donor along with naphthalene (nap) as the acceptor is reported. The co-crystal [systematic name: 1,2,4,5-tetra-chloro-3,6-di-iodo-benzene-naphthalene, (CICl)·(nap)] generates a chevron-like structure that is held together primarily by π-type halogen bonds (. C-I⋯π contacts) between the components.

Sequential Deoxygenation of CO and NO via Redox-Control of a Pyridinediimine Ligand with a Hemilabile Phosphine.

The deoxygenation of environmental pollutants CO and NO to form value-added products is reported. CO reduction with subsequent CO release and NO conversion to NO are achieved via the starting complex Fe(PDI)Cl (). contains the redox-active pyridinediimine (PDI) ligand with a hemilabile phosphine located in the secondary coordination sphere.

Photochemical reactions of a diamidocarbene: cyclopropanation of bromonaphthalene, addition to pyridine, and activation of sp C-H bonds.

We report unprecedented photochemistry for the diamidocarbene 1. Described within are the double cyclopropanation of 1-bromonaphthalene, the double addition to pyridine, and remarkably, the insertion into the unactivated sp C-H bonds of cyclohexane, tetramethylsilane, and -pentane to give compounds 2-6, respectively. All compounds have been fully characterized, and the solid state structure of 4 was obtained using single crystal electron diffraction.

Colossal Anisotropic Thermal Expansion in a Diazo-Functionalized Compound with Switchable Solid-State Behavior.

Achieving substantial anisotropic thermal expansion (TE) in solid-state materials is challenging as most materials undergo volumetric expansion upon heating. Here, we describe colossal, anisotropic TE in crystals of an organic compound functionalized with two azo groups. Interestingly, the material exhibits distinct and switchable TE behaviors within different temperature regions.

Triple-Decker Iron and Cobalt Complexes Featuring a Bridging 1,2-Diboratabenzene Ligand.

Neutral triple-decker iron and cobalt complexes with a bridging 1,2-diboratabenzene ligand were accessed by reactions of a dilithium 1,2-diboratabenzene reagent with [Cp*FeCl] and [Cp*CoCl], respectively. While 1,2-diboratabenzene metal complexes are known, these represent the first examples of the ligand bridging two metals.

-Di-chlorido-tetra-kis-(4-meth-oxy-pyridine-κ)ruthenium(II).

The structure of the title complex, [RuCl(CHNO)], exhibits point group symmetry . The structure exhibits disorder around a axis. The 4-meth-oxy-pyridine ligands have a propeller-like arrangement around the Ru atom at 52.

Dimethyl 4,5-di-chloro-phthalate.

While endeavoring to synthesize new chlorinated ligands for ruthenium-based metathesis catalysts, the title compound dimethyl 4,5-di-chloro-phthalate, CHClO, was prepared from commercially available 4,5-di-chloro-phthalic acid in ∼77% yield. The title mol-ecule, which also finds utility as a precursor mol-ecule for the synthesis of drugs used in the treatment of Alzheimer's disease, shows one carbonyl-containing methyl ester moiety lying nearly co-planar with the chlorine-derivatized aromatic ring while the second methyl ester shows a significant deviation of 101.05 (12)° from the least-squares plane of the aromatic ring.

Crystal structures of anhydrous and hydrated -benzyl-cinchonidinium bromide.

-benzyl-cinchonidinium bromide, CHNO·Br, with the systematic name ()-[(2,4,5)-1-benzyl-5-ethenyl-1-azoniabi-cyclo-[2.2.2]octan-2-yl](quinolin-4-yl)-methanol bromide, is a quaternary ammonium salt of the alkaloid cinchonidine.

Crystal structure of 1-imidazole-1-methanol.

The synthesis and the crystal structure of 1-imidazole-1-methanol, CHNO, are described. This compound comprises an imidazole ring with a methanol group attached at the 1-position affording an imine nitro-gen atom able to receive a hydrogen bond and an alcohol group able to donate to a hydrogen bond. This imidazole methanol crystallizes with monoclinic (2/) symmetry with three symmetry-unique mol-ecules.

Halogen-Bond Mediated [2+2] Photodimerizations: À la Carte Access to Unsymmetrical Cyclobutanes in the Solid State.

The ditopic halogen-bond (X-bond) donors 1,2-, 1,3-, and 1,4-diiodotetrafluorobenzene (, , and , respectively) form binary cocrystals with the unsymmetrical ditopic X-bond acceptor -1-(2-pyridyl)-2-(4-pyridyl)ethylene (). The components of each cocrystal ()·(), ()·(), and ()·() assemble via N···I X-bonds. For ()·() and ()·(), the X-bond donor supports the C=C bonds of to undergo a topochemical [2+2] photodimerization in the solid state: UV-irradiation of each solid resulted in stereospecific, regiospecific, and quantitative photodimerization of to the corresponding head-to-tail () or head-to-head () cyclobutane photoproduct, respectively.

Synthesis and structure determination of racemic (Δ/Λ)-tris-(ethyl-enedi-amine)-cobalt(III) trichloride hemi(hexa-aqua-sodium chloride).

The synthesis and crystal structure of the title racemic compound, [Co(CHN)]Cl.{[Na(HO)]Cl}, are reported. The trivalent cobalt atom, which resides on a crystallographic threefold axis, is chelated by a single ethyl-ene di-amine (en) ligand and yields the tris-chelate [Co(en)] cation with distorted octa-hedral geometry after the application of crystal symmetry.

IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions.

Conjugated molecular chains have the potential to act as "molecular wires" that can be employed in a variety of technologies, including catalysis, molecular electronics, and quantum information technologies. Their successful application relies on a detailed understanding of the factors governing the electronic energy landscape and the dynamics of electrons in such molecules. We can gain insights into the energetics and dynamics of charges in conjugated molecules using time-resolved infrared (TRIR) detection combined with pulse radiolysis.

NO Coupling by Nonclassical Dinuclear Dinitrosyliron Complexes to Form NO Dictated by Hemilability.

Selective coupling of NO by a nonclassical dinuclear dinitrosyliron complex (D-DNIC) to form NO is reported. The coupling is facilitated by the pyridinediimine (PDI) ligand scaffold, which enables the necessary denticity changes to produce mixed-valent, electron-deficient tethered DNICs. One-electron oxidation of the [{Fe(NO)}] complex Fe(PDI)(NO) () results in NO coupling to form NO via the mixed-valent {[Fe(NO)]} species, which possesses an electron-deficient four-coordinate {Fe(NO)} site, crucial in N-N bond formation.

Self-Assembly of Diboronic Esters with U-Shaped Bipyridines: "Plug-in-Socket" Assemblies.

Self-assembled complexes utilizing the ditopic dative bond acceptor 1,3-diboronic acid with catechol and complementary U-shaped donors in the form of 1,8-dipyridylnaphthalenes (1,8-bis(4-pyridyl)naphthalene (), 1,8-bis(4-ethylenylpyridyl)naphthalene (), and 1,8-bis(4-ethynylpyridyl)naphthalene ()) yielded discrete two-component structures. The assemblies exhibit "plug-in-socket" geometries. DFT calculations are consistent with the donor pyridyl and acceptor catecholate being electron poor and rich, respectively.

Square network based upon the molecular salt of the tetraprotonated photoproduct rtct-tetrakis(pyridin-4-yl)cyclobutane and the sulfate anion.

The formation and crystal structure of a hydrated molecular salt that results in a square network is reported. The crystalline solid is based upon the tetraprotonated photoproduct rtct-tetrakis(pyridin-4-yl)cyclobutane (4H-rtct-TPCB) along with two sulfate anions (SO) and eight waters of hydration, namely, 4,4',4'',4'''-(cyclobutane-1,2,3,4-tetrayl)tetrapyridinium bis(sulfate) octahydrate, CHN·2SO·8HO. The fully protonated photoproduct acts as a four-connecting node within the square network by engaging in four charge-assisted N-H.

Synthesis, crystal structure determination, and spectroscopic analyses of 1-chloro-2-(2,6-diisopropylphenyl)-4,4-dimethyl-2-azaspiro[5.5]undecane-3,5-dione: an unyielding precursor to a cyclic (alkyl)(amido)carbene.

The synthesis, single-crystal X-ray structure, and H and C NMR spectrocopic analyses of an unyielding precursor molecule to a cyclic (alkyl)(amido)carbene, 1-chloro-2-(2,6-diisopropylphenyl)-4,4-dimethyl-2-azaspiro[5.5]undecane-3,5-dione, CHClNO (1), is reported. Despite the use of several bases, 1 could not be deprotonated to afford the corresponding carbene.