Self-assembly of a unique hexadecanuclear [4 x (2 x 2)]-Pb16 'grid of grids' type structure

A new ligand containing a linear sequence of four-tridentate chelating subunits built around alkoxide and pyrimidine bridging groups undergoes a spontaneous self-assembly process with Pb(CF3SO3)2 to produce a unique hexadecanuclear [4 x (2 x 2)] 'grid of grids' type structure with external dimensions of 26 A.     

Effects of swirl on flow separation and performance of wide angle diffusers

Experimental investigations have been carried out to determine whether the introduction of a circumferential velocity component can produce worthwhile improvements in the performance of, and eliminate flow separation in, wide angle conical diffusers. The swirl generator is a 24 flat-bladed, radial intake type. Systematic experimentation has been carried out for one diffuser configuration fitted with a tailpipe (16.5° and 4.4 area ratio) using varying strengths of inlet swirl and introducing the dissipated mechanical energy as the main criterion of diffuser performance. The best inlet swirl strength produced about 60% reduction of the total diffuser losses in swirl-free flow. The analysis of these results, together with information obtained from flow visualisation experiments, suggests that increasing the swirl beyond an observed threshold completely eliminated flow separation, but it also gave rise to a central zone of recirculating flow and hence additional dissipative losses. We conclude that the optimum improvement achievable in wide angle diffuser performance using swirl does not require the addition of more energy than it saves     

Wave-particle dualism and the interpretation of quantum mechanics

The realist interpretations of quantum theory, proposed by de Broglie and by Bohm, are re-examined and their differences, especially concerning many-particle systems and the relativistic regime, are explored. The impact of the recently proposed experiments of Vigier et al. and of Ghose et al. on the debate about the interpretation of quantum mechanics is discussed. An indication of how de Broglie and Bohm would account for these experimental results is given.     

Intramolecular diels-alder cycloadditions of bis-diene substrates

Unique internal competition in the intramolecular cycloaddition of bis-diene substrates occurs with high stereoselectivity. Aqueous reaction conditions promote coiling of the lipophilic chain which alters the observed regioselectivity.     

Resolvable path designs

A resolvable (balanced) path design, RBPD(v, k, λ) is the decomposition of λ copies of the complete graph on v vertices into edge-disjoint subgraphs such that each subgraph consists of $\text{v}\text{k}$ vertex-disjoint paths of length k ? 1 (k vertices). It is shown that an RBPD(v, 3, λ) exists if and only if v ≡ 9 (modulo 12/gcd(4, λ)). Moreover, the RBPD(v, 3, λ) can have an automorphism of order $\text{v}\text{3}$. For k > 3, it is shown that if v is large enough, then an RBPD(v, k, 1) exists if and only if v ≡ k² (modulo lcm(2k ? 2, k)). Also, it is shown that the categorical product of a k-factorable graph and a regular graph is also k-factorable. These results are stronger than two conjectures of P. Hell and A. Rosa     

Triclinic and monoclinic polymorphs of meso‐(E,E)‐1,1′‐[1,2‐bis(4‐chlorophenyl)ethane‐1,2‐diyl]bis(phenyldiazene): the high‐yield synthesis of an unexpected product,concomitant polymorphism and configurational disorder

Pyrazolidine‐3,5‐diones and their derivatives exhibit a wide range of biological activities. Seeking to explore the effect of combining a hydrocarbyl ring substituent, as present in sulfinpyrazone (used to treat gout), with a chlorinated aryl ring, as present in muzolimine (a diuretic), we explored the reaction between 1‐phenylpyrazolidine‐3,5‐dione and 4‐chlorobenzaldehyde under mildly basic conditions in the expectation of producing the simple condensation product 4‐(4‐chlorobenzylidene)‐1‐phenylpyrazolidine‐3,5‐dione. However, the reaction product proved to be meso‐(E,E)‐1,1′‐[1,2‐bis(4‐chlorophenyl)ethane‐1,2‐diyl]bis(phenyldiazene), C₂₆H₂₀Cl₂N₄, and a tentative mechanism is proposed. Crystallization from ethanol produces two concomitant polymorphs, i.e. a triclinic form, (I), in the space group P, and a monoclinic form, (II), in the space group C2/c. In both polymorphs, the molecules lie across centres of inversion, but in (II), the molecules are subject to whole‐molecule disorder equivalent to configurational disorder with occupancies of 0.6021 (19) and 0.3979 (19). There are no hydrogen bonds in the crystal structure of polymorph (I), but the molecules of polymorph (II) are linked by C—H...π(arene) hydrogen bonds into complex chains, which are further linked into sheets by C—H...N interactions.     

Mixed valence Mn(II)/Mn(III) [3 x 3] grid complexes: structural, electrochemical, spectroscopic, and magnetic properties

Mn(II)9 grid complexes with a [Mn9(mu-O)12] core, obtained by self-assembly of a series of tritopic picolinic dihydrazone ligands with Mn(II) salts, have been oxidized by both chemical and electrochemical methods to produce mixed oxidation state systems. Examples involving [Mn(III)3Mn(II)6] and [Mn(III)4Mn(II)5] combinations have been produced. Structures are reported for [Mn9(2poap-2H)6](NO3)6.14H2O (1), [Mn9(2poap-2H)6](ClO4)10.10H2O (3), and [Mn9(Cl2poap-2H)6](ClO4)9.14H2O.3CH3CN (10). Structural studies show distinct contraction of the corner grid sites on oxidation, with overall magnetic properties consistent with the resulting changes in electron distribution. Antiferromagnetic exchange in the outer ring of eight metal centers creates a ferrimagnetic subunit, which undergoes antiferromagnetic coupling to the central metal, leading to S=1/2 (3) and S2/2 (10) ground states. Two moderately intense absorptions are observed on oxidation of the Mn(II) grids in the visible and near-infrared (1000 nm, 700 nm), associated with charge transfer transitions (LMCT, IVCT respectively). Compound 1 crystallized in the monoclinic system, space group P2 1/n, with a=21.308(2) A, b=23.611(2) A, c=32.178(3) A, beta=93.820(2) degrees . Compound 3 crystallized in the tetragonal system, space group I, with a=b=18.44410(10) A, c = 24.9935(3) A. Compound 10 crystallized in the triclinic system, space group P, with a=19.1150(10) A, b=19.7221(10) A, c=26.8334(14) A, alpha=74.7190(10) degrees, beta=77.6970(10) degrees, gamma=64.7770(10) degrees. The facile oxidation of the Mn(II)9 grids is highlighted in terms of their potential use as molecular based platforms for switching and data storage.