Di- and tetra-nuclear copper(II), nickel(II), and cobalt(II) complexes of four bis-tetradentate triazole-based ligands: synthesis, structure, and magnetic properties

Four bis-tetradentate N(4)-substituted-3,5-{bis[bis-N-(2-pyridinemethyl)]aminomethyl}-4H-1,2,4-triazole ligands, L(Tz1)-L(Tz4), differing only in the triazole N(4) substituent R (where R is amino, pyrrolyl, phenyl, or 4-tertbutylphenyl, respectively) have been synthesized, characterized, and reacted with M(II)(BF(4))(2)·6H(2)O (M(II) = Cu, Ni or Co) and Co(SCN)(2). Experiments using all 16 possible combinations of metal salt and L(TzR) were carried out: 14 pure complexes were obtained, 11 of which are dinuclear, while the other three are tetranuclear. The dinuclear complexes include two copper(II) complexes, [Cu(II)(2)(L(Tz2))(H(2)O)(4)](BF(4))(4) (2), [Cu(II)(2)(L(Tz4))(BF(4))(2)](BF(4))(2) (4); two nickel(II) complexes, [Ni(II)(2)(L(Tz1))(H(2)O)(3)(CH(3)CN)](BF(4))(4)·0.5(CH(3)CN) (5) and [Ni(II)(2)(L(Tz4))(H(2)O)(4)](BF(4))(4)·H(2)O (8); and seven cobalt(II) complexes, [Co(II)(2)(L(Tz1))(μ-BF(4))](BF(4))(3)·H(2)O (9), [Co(II)(2)(L(Tz2))(μ-BF(4))](BF(4))(3)·2H(2)O (10), [Co(II)(2)(L(Tz3))(H(2)O)(2)](BF(4))(4) (11), [Co(II)(2)(L(Tz4))(μ-BF(4))](BF(4))(3)·3H(2)O (12), [Co(II)(2)(L(Tz1))(SCN)(4)]·3H(2)O (13), [Co(II)(2)(L(Tz2))(SCN)(4)]·2H(2)O (14), and [Co(II)(2)(L(Tz3))(SCN)(4)]·H(2)O (15). The tetranuclear complexes are [Cu(II)(4)(L(Tz1))(2)(H(2)O)(2)(BF(4))(2)](BF(4))(6) (1), [Cu(II)(4)(L(Tz3))(2)(H(2)O)(2)(μ-F)(2)](BF(4))(6)·0.5H(2)O (3), and [Ni(II)(4)(L(Tz3))(2)(H(2)O)(4)(μ-F(2))](BF(4))(6)·6.5H(2)O (7). Single crystal X-ray structure determinations revealed different solvent content from that found by microanalysis of the bulk sample after drying under a vacuum and confirmed that 5', 8', 9', 11', 12', and 15' are dinuclear while 1' and 7' are tetranuclear. As expected, magnetic measurements showed that weak antiferromagnetic intracomplex interactions are present in 1, 2, 4, 7, and 8, stabilizing a singlet spin ground state. All seven of the dinuclear cobalt(II) complexes, 9-15, have similar magnetic behavior and remain in the [HS-HS] state between 300 and 1.8 K.     

Geodesic knots in closed hyperbolic 3-manifolds

We consider the existence of simple closed geodesics or “geodesic knots” in finite volume orientable hyperbolic 3-manifolds. Every such manifold contains at least one geodesic knot by results of Adams, Hass and Scott in (Adams et al. Bull. London Math. Soc. 31: 81–86, 1999). In (Kuhlmann Algebr. Geom. Topol. 6: 2151–2162, 2006) we showed that every cusped orientable hyperbolic 3-manifold in fact contains infinitely many geodesic knots. In this paper we consider the closed manifold case, and show that if a closed orientable hyperbolic 3-manifold satisfies certain geometric and arithmetic conditions, then it contains infinitely many geodesic knots. The conditions on the manifold can be checked computationally, and have been verified for many manifolds in the Hodgson-Weeks census of closed hyperbolic 3-manifolds. Our proof is constructive, and the infinite family of geodesic knots spiral around a short simple closed geodesic in the manifold.      

A robust optimization model for multi-site production planning problem in an uncertain environment

This paper addresses the multi-site production planning problem for a multinational lingerie company in Hong Kong subject to production import/export quotas imposed by regulatory requirements of different nations, the use of manufacturing factories/locations with regard to customers’ preferences, as well as production capacity, workforce level, storage space and resource conditions at the factories. In this paper, a robust optimization model is developed to solve multi-site production planning problem with uncertainty data, in which the total costs consisting of production cost, labor cost, inventory cost, and workforce changing cost are minimized. By adjusting penalty parameters, production management can determine an optimal medium-term production strategy including the production loading plan and workforce level while considering different economic growth scenarios. The robustness and effectiveness of the developed model are demonstrated by numerical results. The trade-off between solution robustness and model robustness is also analyzed.     

Analytical chemistry of synthetic routes to psychoactive tryptamines. Part III. Characterisation of the Speeter and Anthony route to N,N-dialkylated tryptamines using CI-IT-MS-MS

Twelve symmetrically and 13 asymmetrically N,N-disubstituted glyoxalylamide precursors and their corresponding tryptamine derivatives have been characterised by gas chromatography low-pressure chemical ionisation ion trap tandem mass spectrometry (CI-IT-MS-MS) with internal (in situ) ionisation using methanol as the chemical ionisation reagent. Mass spectral differences and similarities between the investigated compounds are discussed and put into context with previous investigations. In tryptamines the formation of [CH2=N+R2R3] iminium ions after beta-cleavage appears to be the dominating process. Dissociation of the protonated molecule into [3-vinylindole]+ for example, appears to be a minor pathway when compared with electrospray triple quadrupole tandem mass spectrometry (ESI-TQ-MS-MS) where this ion transition was found to be of distinctive importance. CI-IT-MS-MS is also found to enable the differentiation between most isomeric derivatives studied.     

Coordination, organometallic and related chemistry of tris(pyrazolyl)methane ligands

Tris(pyrazolyl)methanes are the neutral analogues of the widely exploited and highly useful tris(pyrazolyl)hydroborates, yet by comparison with their boron based counterparts their chemistry is underdeveloped. Recent breakthroughs in the synthesis of ring-substituted tris(pyrazolyl)methanes offer the opportunity for the development of this useful and promising class of ligand. This review summarises the current state of the coordination and organometallic chemistry of tris(pyrazolyl)methanes and highlights areas in which development is likely to occur.     

Photoelectron spectra of bis-cyclopentadienyl metal dihalides

He(I) and HE(II) photoelectron spectra are reported for (η-C₅H₅)₂MX₂ (M = Ti; X = F, Cl, Br, I: M = Zr, Hf; X = Cl, Br: M = Ta; X = Cl, Br) and (η-MeC₅H₄)₂MX₂ (M = Nb, X = Cl: M = Mo; X = Cl, Br, I). A substantial variation is found in the ordering of the halogen and cyclopentadienyl ionizations, the order being dependent on the metal as well as on the halogen. The compounds may be divided into three classes, namely, those in which the electrons in cyclopentadienyl e₁ orbitals ionize at a lower energy than those occupying halogen pπ orbitals, those in which halogen pπ electrons have lower ionization energy than cyclopentadienyl e₁ electrons and those in which the corresponding electrons arise from extensively delocalized molecular orbitals with significant contributions from both these categories of fragment orbital.     

A 2.5-D dynamic model for a saturated porous medium: Part I. Green’s function

Based on Biot’s theory, the dynamic 2.5-D Green’s function for a saturated porous medium is obtained using the Fourier transform and the potential decomposition methods. The 2.5-D Green’s function corresponds to the solutions for the following two problems: the point force applied to the solid skeleton, and the dilatation source applied within the pore fluid. By performing the Fourier transform on the governing equations for the 3-D Green’s function, the governing differential equations for the two parts of the 2.5-D Green’s function are established and then solved to obtain the dynamic 2.5-D Green’s function. The derived 2.5-D Green’s function for saturated porous media is verified through comparison with the existing solution for 2.5-D Green’s function for the elastodynamic case and the closed-form 3-D Green’s function for saturated porous media. It is further demonstrated that a simple form 2-D Green’s function for saturated porous media can be been obtained using the potential decomposition method.     

Verification and validation of a winter driving simulator

A full vehicle dynamics simulator was constructed in SimCreator^® for the Cold Regions Research and Engineering Laboratory (CRREL) Instrumented Vehicle (CIV) and was used to investigate and validate the newly developed Vehicle Terrain Interaction (VTI) code. The VTI code replaces the tire component of the simulated vehicle, in the Driver and Motion Simulator (DMS), allowing it to report back realistic values while driving on various types of terrain surfaces such as mud, snow, ice, and pavement. The validation effort within this paper is focused on the winter (snow and ice) parts of the VTI code. The outputs from the Engineering Research and Development Center (ERDC) and the DMS VTI codes were validated through field experiments and against the North Atlantic Treaty Organization (NATO) Reference Mobility Model (NRMM). The DMS VTI code can be used with different vehicle models, providing the US. Army with a valuable asset that will allow simulation of existing or conceptual, manned or autonomous, ground vehicle performance for acquisition, planning, or training. This information, along with some basic terrain information, will allow troops to plan the fastest and most effective way of getting to a desired location, while minimizing the possibility of being delayed because of the terrain conditions.