Synthesis of perfluoro[2.2]paracyclophane

A synthesis of perfluoro[2.2]paracyclophane has been sought ever since the partially fluorinated octafluoro[2.2]paracyclophane (AF4) was prepared and its chemistry studied. This compound has now been prepared in 39% yield from the precursor, 1,4-bis(chlorodifluoromethyl)-2,3,5,6-tetrafluorobenzene by its reaction with Zn when heated in acetonitrile at 100 degrees C. Two preparations of the precursor, first from 1,4-dicyano-2,3,5,6-tetrachlorobenzene and an improved method beginning from 1,2,4,5-tetrachlorobenzene, are also described as are key comparisons to our related synthesis of AF4.     

Intra- and intermolecular NMR studies on the activation of arylcyclometallated hafnium pyridyl-amido olefin polymerization precatalysts

Pyridyl-amido catalysts have emerged recently with great promise for olefin polymerization. Insights into the activation chemistry are presented in an initial attempt to understand the polymerization mechanisms of these important catalysts. The activation of C1-symmetric arylcyclometallated hafnium pyridyl-amido precatalysts, denoted Me2Hf{N(-),N,C(-)} (1, aryl = naphthyl; 2, aryl = phenyl), with both Lewis (B(C6F5)3 and [CPh3][B(C6F5)4]) and Br?nsted ([HNR3][B(C6F5)4]) acids is investigated. Reactions of 1 with B(C6F5)3 lead to abstraction of a methyl group and formation of a single inner-sphere diastereoisomeric ion pair [MeHf{N(-),N,C(-)}][MeB(C6F5)3] (3). A 1:1 mixture of the two possible outer-sphere diastereoisomeric ion pairs [MeHf{N(-),N,C(-)}][B(C6F5)4] (4) is obtained when [CPh3][B(C6F5)4] is used. [HNR3][B(C6F5)4] selectively protonates the aryl arm of the tridentate ligand in both precatalysts 1 and 2. A remarkably stable [Me2Hf{N(-),N,C2}][B(C6F5)4] (5) outer-sphere ion pair is formed when the naphthyl substituent is present. The stability is attributed to a hafnium/eta(2)-naphthyl interaction and the release of an eclipsing H-H interaction between naphthyl and pyridine moieties, as evidenced through extensive NMR studies, X-ray single crystal investigation and DFT calculations. When the aryl substituent is phenyl, [Me2Hf{N(-),N,C2}][B(C6F5)4] (10) is originally obtained from protonation of 2, but this species rapidly undergoes remetalation, methane evolution, and amine coordination, giving a diastereomeric mixture of [MeHf{N(-),N,C(-)}NR3][B(C6F5)4] (11). This species transforms over time into the trianionic-ligated [Hf{N(-),C(-),N,C(-)}NR3][B(C6F5)4] (12) through activation of a C-H bond of an amido-isopropyl group. In contrast, ion pair 5 does not spontaneously undergo remetalation of the naphthyl moiety; it reacts with NMe2Ph leading to [MeHf{N(-),N}NMe2C6H4][B(C6F5)4] (7) through ortho-metalation of the aniline. Ion pair 7 successively undergoes a complex transformation ultimately leading to [Hf{N(-),C(-),N,C(-)}NMe2Ph][B(C6F5)4] (8), strictly analogous to 12. The reaction of 5 with aliphatic amines leads to the formation of a single diastereomeric ion pair [MeHf{N(-),N,C(-)}NR3][B(C6F5)4] (9). These differences in activation chemistry are manifested in the polymerization characteristics of these different precatalyst/cocatalyst combinations. Relatively long induction times are observed for propene polymerizations with the naphthyl precatalyst 1 activated with [HNMe3Ph][B(C6F5)4]. However, no induction time is present when 1 is activated with Lewis acids. Similarly, precatalyst 2 shows no induction period with either Lewis or Br?nsted acids. Correlation of the solution behavior of these ion pairs and the polymerization characteristics of these various species provides a basis for an initial picture of the polymerization mechanism of these important catalyst systems.     

Spin maximization: switching of the usual S = 11 state of Mn(II)4Mn(III)3 disklike complexes to the maximum S = 16

The S = 11 ground states of the Mn 7 family of mixed-valence complexes with a metal-centered hexagonal topology have been found by density functional theory calculations to arise by spin frustration involving small differences in the magnitudes of the two weakest interactions controlling the alignment of the central spin. Targeted structural perturbation has allowed a complex with the central spin flipped to be discovered, which thus possesses the maximum S = 16 ground state.     

Single-molecule magnetism properties of the first strontium-manganese cluster [SrMn14O11(OMe)3(O2CPh)18(MeCN)2

The preparation and properties of the first strontium-manganese molecular complex are described. The reaction of (NBu(n)4)[Mn4O2(O2CPh)9(H 2O)] (4Mn(III)) with Sr(ClO4)2 in MeCN/MeOH led to the isolation of [SrMn14O11(OMe)3(O2CPh)18(MeCN)2] ( 1; 13Mn(III), Mn(II)). The structure of 1 consists of two [Mn4O3(OMe)] cubane units attached to a central, near-planar, trinuclear [Mn3O4] unit, to which are also attached a Mn and a Sr above the plane and a [Mn2O(OMe)] rhomb below the plane. Peripheral ligation is provided by 18 bridging benzoate and two terminal MeCN groups. Variable-temperature and -field dc magnetization (M) data were collected in the 1.8-10 K and 0.1-4.0 T ranges and fit by matrix diagonalization methods to give S = 9/2, D = -0.50(5) cm(-1), and g = 1.88(10), where S is the ground-state spin and D is the axial zero-field splitting parameter. Magnetization versus dc field sweeps at various temperatures and scan rates exhibited hysteresis loops, confirming 1 to be a new single-molecule magnet. Because complex 1 is the initial molecular example of intimately associated Mn and Sr atoms, Sr EXAFS studies have been performed for the first time on a synthetic Sr-containing molecule. This has also allowed comparisons with the EXAFS data on the Sr-substituted water oxidizing complex (WOC) of Photosystem II (PS II), which contains a SrMn4 complex.     

Synthesis of electronically diverse tetraarylimidazolylidene carbenes via catalytic aldimine coupling

A new method for synthesizing symmetrical N-heterocyclic imidazolium salts is described. Catalytic coupling of aldimines with cyanide followed by oxidation gives alpha-diketimines, which can then be cyclized with formaldehyde in acidic media. This two-step procedure requires no chromatography and allows the synthesis of electronically diverse 1,3,4,5-tetraarylimidazolylidene carbenes.     

Axial field shaping under high-numerical-aperture focusing

Kant reported [J. Mod. Optics 47, 905 (2000)] a formulation for solving the inverse problem of vector diffraction, which accurately models high-NA focusing. Here, Kant's formulation is adapted to the method of generalized projections to obtain an algorithm for designing diffractive optical elements (DOEs) that reshape the axial point-spread function (PSF). The algorithm is applied to design a binary phase-only DOE that superresolves the axial PSF with controlled increase in axial sidelobes. An 11-zone DOE is identified that axially narrows the PSF central lobe by 29% while maintaining the sidelobe intensity at or below 52% of the peak intensity. This DOE could improve the resolution achievable in several applications without significantly complicating the optical system.     

Simple Systems with Anomalous Dissipation and Energy Cascade

We analyze a class of dynamical systems of the type where f _n (t) is a forcing term with only for and the coupling coefficients c _n satisfy a condition ensuring the formal conservation of energy . Despite being formally conservative, we show that these dynamical systems support dissipative solutions (suitably defined) and, as a result, may admit unique (statistical) steady states when the forcing term f _n (t) is nonzero. This claim is demonstrated via the complete characterization of the solutions of the system above for specific choices of the coupling coefficients c _n . The mechanism of anomalous dissipations is shown to arise via a cascade of the energy towards the modes with higher n; this is responsible for solutions with interesting energy spectra, namely scales as as n→∞. Here the exponents α depend on the coupling coefficients c _n and denotes expectation with respect to the equilibrium measure. This is reminiscent of the conjectured properties of the solutions of the Navier-Stokes equations in the inviscid limit and their accepted relationship with fully developed turbulence. Hence, these simple models illustrate some of the heuristic ideas that have been advanced to characterize turbulence, similar in that respect to the random passive scalar or random Burgers equation, but even simpler and fully solvable.     

A discrete Fe18 'molecular chain'

The use of a new O,N,N,O chelate has led to two new Fe6 and Fe18 molecular compounds, the latter with an unusual double-headed serpentine chain structure.     

A Family of 3-D Coordination Polymers Composed of Mixed-Valence Mn6 Octahedra within Na4 Tetrahedra

The combined use of 1,1,1-tris(hydroxymethyl)ethane (thmeH₃) and azides in Mn carboxylate chemistry has yielded a new family of decanuclear [Mn₆Na₄O(N₃)(O₂CR)₅(thme)₄(H₂O)₄] (R = Me (1); Et (2)) complexes consisting of mixed-valence Mn ₂ ^II Mn ₄ ^III units with a very rare [Mn₆(μ₆-O)]¹⁴⁺ octahedral core contained within a tetrahedron of four Na^I atoms. The [Mn₆Na₄] units of 1 and 2 are connected via the Na atoms to neighboring units, giving 3-D supramolecular assemblies with large channel cavities. Variable-temperature, solid-state dc and ac magnetization studies carried out in the 1.8–300 K range reveal that the Mn₆ units of 1 and 2 are antiferromagnetically coupled to give S = 0 ground states for both complexes.     

X-ray fluorescence analysis for the study of fragments pottery excavated at Tell Jendares site, Syria, employing multivariate statistical analysis

X-ray fluorescence analysis study of 44 archaeological pottery samples collected from Tell Jendares site north-west of Syria has been carried out. Four samples of the total previous investigated samples were obtained from the kiln found on Tell Jendares site. Seventeen different chemical elements were determined. The XRF results have been processed using two multivariate statistical cluster and factor analysis methods in order to determine the similarities and correlation between the selected samples based on their elemental composition. The methodology successfully separates the samples where three distinct chemical groups were discerned.