A shape-optimization technique for the capillary surface problem

Summary The problem of the construction of an equilibrium surface taking the surface tension into account leads to Laplace-Young equation which is a nonlinear elliptic free-boundary problem. In contrast to Orr et al. where an iterative technique is used for direct solution of the equation for problems with simple geometry, we propose here an alternative approach based on shape optimization techniques. The shape of the domain of the liquid is varied to attain the optimality condition. Using optimal control theory to derive expressions for the gradient, a numerical scheme is proposed and simple model problems are solved to validate the scheme.     

Towards an enantiospecific total synthesis of garsubellin A and related phloroglucin natural products: the α-pinene approach

The first enantiospecific approach to garsubellin A and related phloroglucin natural product nemorosone, of contemporary interest from (−)-α-pinene, has been delineated. Through a series of stereospecific operations, the requisite stereochemistry of the prenyl groups has been secured. Kende cyclization has been employed as the key step to construct the functionalized bicyclo[3.3.1]nonane core.     

Self-assembled metallasupramolecular cages towards light harvesting systems for oxidative cyclization

Designing artificial light harvesting systems with the ability to utilize the output energy for fruitful application in aqueous medium is an intriguing topic for the development of clean and sustainable energy. We report here facile synthesis of three prismatic molecular cages as imminent supramolecular optoelectronic materials via two-component coordination-driven self-assembly of a new tetra-imidazole donor (L) in combination with 180°/120° di-platinum(ii) acceptors. Self-assembly of 180° trans-Pt(ii) acceptors A1 and A2 with L leads to the formation of cages Pt₄L₂(1a) and Pt₈L₂(2a) respectively, while 120°-Pt(ii) acceptor A3 with L gives the Pt₈L₂(3a) metallacage. PF₆⁻ analogues (1b, 2b and 3b) of the metallacages possess a high molar extinction coefficient and large Stokes shift. 1b–3b are weakly emissive in dilute solution but showed aggregation induced emission (AIE) in a water/MeCN mixture as well as in the solid state. AIE active 2b and 3b in aqueous (90% water/MeCN mixture) medium act as donors for fabricating artificial light harvesting systems via Förster resonance energy transfer (FRET) with organic dye rhodamine-B (RhB) with high energy efficiency and good antenna effect. The metallacages 2b and 3b represent an interesting platform to fabricate new generation supramolecular aqueous light harvesting systems with high antenna effect. Finally, the harvested energy of the LHSs (2b + RhB) and (3b + RhB) was utilized successfully for efficient visible light induced photo-oxidative cross coupling cyclization of N,N-dimethylaniline (4) with a series of N-alkyl/aryl maleimides (5) in aqueous acetonitrile with dramatic enhancement in yields compared to the reactions with RhB or cages alone.

Synthesis of Pt(ii) based metallacages as aggregation induced emissive supramolecular architectures for fabricating artificial light harvesting systems for cross coupling cyclization under visible light is achieved.     

Kinetics and mechanism of the reaction oftrans-cyclohexane-1,2-diamine-N N N' N'-tetra-acetatomanganate(III) with substituted thioureas in aqueous medium

Summary The kinetics of reduction of [Mn^III(cydta)]^– (where H₄cydta=trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5–4.5 and 9.2–10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the Mn^III complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects.     

Coordination chemistry of f-block elements with imine acids. Part IV. Synthetic and chiroptical studies on lanthanide(III) complexes of imine acids derived from L-alanine,L-valine,L-tyrosine and L-glutamic acid

Summary N-(orthovanillidene)L-alanine (OVAlaH₂), N-(salicylidene)L-valine (SValH₂), N-(orthovanillidene)L-valine (OVValH₂), N-(orthovanillidene)L-tyrosine (OVTyrH₃) and N-(salicylidene)L-glutamic acid (SGluH₃) react with La^III, Pr^III, Nd^III and Sm^III to yield new chiral complexes. Their dominant conformers were determined from c.d. spectra supported by¹H n.m.r. data, except for the L-glutamic acid derived complexes which were insoluble.     

Biyclo[2.2.1]heptane as cyclopentane precursor. Part 4 Stereocontrolled syhthesis of a potential intermediate to chromophycane dolastane and clavularane

The regio– and stereoselective synthesis of the keto-esters 20 and 22 are described, the latter being a potential intermediate to several diterpenes. The key steps involve the Diels-Alder cycloaddition between the benzocycloheptenone 5 and cyclopentadiene followed by a regioselective functionalisation of the adduct 6. A remarkable reversal of regioselectivity was observed during oxymercuration of the unsymmetric double bond in 6 and its reduced product 11 leading to 8 and 12 which were subsequently transformed to 20 and 22 respectively.     

Polymerization of vinylcarbazole on copper(II)-13X molecular sieves: Role of copper(II) salts

Copper(II)-exchanged-13X molecular sieves, prepared from four copper(II) salts, namely, sulfate, nitrate, chloride, and acetate, and their activities in the polymerization of N-vinylcarbazole at a fixed copper ion exchange level were studied. From the kinetic characteristics of polymerization it was established that the variation in activities of the Cu-exchanged sieves is due primarily to the difference in the pH of the original salt solution, which is responsible for the varying degree of proton exchange with the zeolite during copper ion exchange. A first-order dependence of the rate of polymerization was observed with respect to H⁺ ion concentration of the original copper-salt solution. It was further established that the rate of polymerization of exchanged copper ion, at a hypothetical zero proton concentration, is low. A mechanism of polymerization of NVC on copper-exchanged-13X zeolite was suggested on the basis of the results obtained.     

Coordination modes of 1-allyl benzotriazole: synthesis and characterization of cobalt(II), nickel(II), copper(II), copper(I) and silver(I) complexes

Summary The synthesis and coordination behaviour of 1-allylbenzotriazole (ABT), containing both -donating heterocyclic ring nitrogen(s) and a -bonding olefinic group, has been studied by complexation with Co^II, Ni^II, Cu^II, Cu^I and Ag^I salts. The solid complexes M(ABT)₂X₂ (M=Co, Ni or Cu and X=a counterion) and M(ABT)X (M=Cu or Ag and X=Br, I, or NO₃) have been characterised by¹H-n.m.r. (representative Cu^I species) and other physical data. Different modes coordination for the title ligand have been proposed based upon i.r. data which indicate the participation of a -donating ring nitrogen only in complexes with bivalent metal salts, and the involvement of both the ring nitrogen and the allylic olefinic component in bonding to a monovalent metal ion.¹H-n.m.r. data are qualitatively commensurate with participation of the allyl group in monovalent metal complexes.     

Reductive nitrosylation of tetraoxometallates—XVII. Molybdate-hydroxylamine-cyanide reaction, and synthesis and characterization of K2[Mo(NO)(CN)5] and (NMe4)2[Mo(NO)(CN)4]

A reaction condition is established which determines the nature of the products in the molybdate-hydroxylamine-cyanide reaction. With hydroxylamine always used in excess, it is the hydroxyl ion concentration of the reaction mixture which plays a vital role in determining whether K₄[Mo(NO)(CN)₅] or K₂[Mo(NO)(CN)₅] is obtained exclusively. The latter product is hereby reported for the first time. Its powder diffractogram being typical of a cubic system, a gross structural characterization has been made possible. The former under aqueous, aerobic conditions yields a new product, (NMe₄)₂[Mo(NO)(CN)₄].     

Kinetic studies of nonaqueous polymerization of methyl methacrylate initiated by ferric laurate–n-hexyl amine system

The polymerization of methyl methacrylate was studied in carbon tetrachloride medium with ferric laurate, a metal soap, in combination with n-hexyl amine as the initiator system at 60°C. The rate of polymerization was found to be linear with the monomer concentration and proportional to the square root of both ferric ion and amine concentration. A reaction scheme involving initial complex formation between ferric ion and amine and subsequent reaction of the complex with the solvent molecule to produce free radicals responsible for initiation of polymerization has been postulated to account for the observed results.