Design, formation and properties of tetrahedral M(4)L(4) and M(4)L(6) supramolecular clusters

The rigid tris- and bis(catecholamide) ligands H(6)A, H(4)B and H(4)C form tetrahedral clusters of the type M(4)L(4) and M(4)L(6) through self-assembly reactions with tri- and tetravalent metal ions such as Ga(III), Fe(III), Ti(IV) and Sn(IV). General design principles for the synthesis of such clusters are presented with an emphasis on geometric requirements and kinetic and thermodynamic considerations. The solution and solid-state characterization of these complexes is presented, and their dynamic solution behavior is described. The tris-catecholamide H(6)A forms M(4)L(4) tetrahedra with Ga(III), Ti(IV), and Sn(IV); (Et(3)N)(8)[Ti(4)A(4)] crystallizes in R3(-)c (No. 167), with a = 22.6143(5) A, c = 106.038(2) A. The cluster is a racemic mixture of homoconfigurational tetrahedra (all Delta or all Lambda at the metal centers within a given cluster). Though the synthetic procedure for synthesis of the cluster is markedly metal-dependent, extensive electrospray mass spectrometry investigations show that the M(4)A(4) (M = Ga(III), Ti(IV), and Sn(IV)) clusters are remarkably stable once formed. Two approaches are presented for the formation of M(4)L(6) tetrahedral clusters. Of the bis(catecholamide) ligands, H(4)B forms an M(4)L(6) tetrahedron (M = Ga(III)) based on an "edge-on" design, while H(4)C forms an M(4)L(6) tetrahedron (M = Ga(III), Fe(III)) based on a "face-on" strategy. K(5)[Et(4)N](7)[Fe(4)C(6)] crystallizes in I43(-)d (No. 220) with a = 43.706(8) A. This M(4)L(6) tetrahedral cluster is also a racemic mixture of homoconfigurational tetrahedra and has a cavity large enough to encapsulate a molecule of Et(4)N(+). This host-guest interaction is maintained in solution as revealed by NMR investigations of the Ga(III) complex.     

Elucidating the Origin of Conformational Energy Differences in Substituted 1,3-Dioxanes: A Combined Theoretical and Experimental Study

13C NMR spectroscopy, ab initio quantum mechanics, and molecular mechanics have been used to investigate the trans-4-(trifluoromethyl)-2,2,6-trimethyl-1,3-dioxane chair/twist-boat equilibrium. The molecular mechanics calculations were based upon the MM3 and AMBER force fields. A 6-31G basis set was used for the ab initio calculations, and MP2 correlation corrections were applied. Both the ab initio and AMBER molecular mechanics calculations are consistent with the (13)C NMR chemical shift differences for the trans-4-(trifluoromethyl)-2,2,6-trimethyl-1,3-dioxane conformers. The predicted chair to twist-boat equilibrium suggested by the MM3 calculations is not consistent with the experimental data. These results support the suggestion by Howard et al. (Howard, A. E.; Cieplak, P.; Kollman, P. A. J. Comput.Chem. 1995, 16, 243-261) on the critical role of electrostatic interactions in determining the chair/twist-boat equilibrium.     

Electrophilic aromatic substitution in the curing of brominated poly(isobutylene-co-4-methylstyrene): A mechanistic model study with zinc salts

The crosslinking chemistry of a new elastomer based on brominated poly(isobutylene-co-4-methylstyrene) has been investigated using model compounds. In order to mimic the conditions that prevail within the highly allphatic rubber, the study was carried out in mineral oil using catalysts that are compatible with such low polarity media. Electrophilic aromatic substitution reactions occur in a system consisting of p-isopropylbenzyl bromide and p-isopropyl toluene in the presence of zinc oxide and zinc stearate. The reaction proceeds after a significant induction period while no induction period is seen for a similar reaction with zinc bromide as the catalyst. The in situ formation of reactive species containing Zn? Br bonds appears to be an important step in the overall process. The stoichiometric ratio of zinc salt to benzylic bromide is important. High ratios lead to the accumulation of benzylic stearate or benzylic alcohol in the system which retards the alkylation reaction. The model study emphasizes the importance of stoichiometry of reagents in this reaction and provides insight into the crosslinking mechanism. © 1993 John Wiley & Sons, Inc.     

Microlaser-pumped periodically poled lithium niobate optical parametric generator-optical parametric amplifier

For what is believed to be the first time, a single-longitudinal-mode passively Q-switched Nd:YAG microlaser is used to pump a narrow-bandwidth periodically poled lithium niobate (PPLN) optical parametric generator-optical parametric amplifier (OPG-OPA). Before amplification in the OPA, the output of the OPG stage was spectrally filtered with an air-spaced etalon, resulting in spectroscopically useful radiation (bandwidth, ~0.05 cm(-1) FWHM) that was tunable in 15-cm(-1) segments anywhere in the signal range 6820-6220 cm(-1) and the idler range 2580-3180 cm(-1). The ability to pump an OPG-OPA with compact, high-repetition-rate, intrinsically narrow-bandwidth microlasers is made possible by the high gain of PPLN. The result is a tunable light source that is well suited for use in portable spectroscopic gas sensors.     

Polyfluorocycloalkenes. Part XV [1]. Reactions of decafluorocyclohexene with secondary amines

Pyrrolidine, 3,3,4,4-tetrafluoropyrrolidine, and dimethylamine, react with decafluorocyclohexene to give the non-basic enamines, 1-pyrrolidino-, 1-(3′,3′,4′,4′-tetrafluoropyrrolidino)-, and 1-dimethylamino-nonafluorocyclohex- 1-ene, respectively.     

Experimental study of pionic Ca and Ti and examination of the pion-nuclear potential for low-Z nuclei

We report the measurement of the strong interaction shifts and widths of the 3d → 2p transitions in pionic ^{40,42,43,44,48}Ca and ^46,48,50Ti. Using these new data in combination with earlier low-Z pionic data (6 ≦ Z ≦ 16), we have studied, in a purely phenomenological way, the pion-nuclear optical potential. Employing nuclear-structure information from Hartree-Fock calculations and measured charge densities, we have fitted the pion-nuclear potential parameters to the pionic atom data. The effect of adding an isovector dependence to the s- and p-wave two-nucleon terms has been investigated. We have also explored the sensitivity of these data to the value of the Lorentz-Lorenz parameter ξ. A small but definite sensitivity to the latter parameter has been observed with the best fit value of ξ being significantly greater than 1. We have used the phenomenological potentials to determine the neutron radii of the Ca and Ti isotopes and, in fact, find reasonable agreement with Hartree-Fock predictions and with the results of other hadronic probes.     

Characterization of the Darboux point for particular classes of problems

A minimal sufficient condition for global optimality involving the Darboux point, analogous to the minimal sufficient condition of local optimality involving the conjugate point, is presented. The Darboux point is then characterized for optimal control problems with linear dynamics, cost functionals with a general terminal state term and an integrand quadratic in the state and control, and general terminal conditions. The Darboux point is shown to be the supremum of a sequence of conjugate points. If the terminal state term is quadratic, along with a scalar quadratic boundary condition, then the Darboux point is also the time at which the Riccati matrix becomes unbounded, giving a characterization of the unboundedness of the Riccati matrix at points which are not in general conjugate points.This research was supported by the National Science Foundation under Grant No. GK-30115.This is Definition 2.1 of Ref. 1.     

Existence of ground states and KMS states for approximately inner dynamics

A strongly continuous one parameter group of *-automorphisms of aC*-algebra with unit is said to be approximately inner if it can be approximated strongly by inner one parameter groups of *-automorphisms. It is shown that an approximately inner one parameter group of *-automorphisms has a ground state and, if there exists a trace state, a KMS state for all inverse temperatures. It follows that quantum lattice systems have ground states and KMS states. Conditions that a strongly continuous one parameter group of *-automorphisms of a UHF algebra be approximately inner are given in terms of the unbounded derivation which generates the automorphism group.     

A precision determination of the radial charge parameters and the quadrupole moment of 181Ta using muonic X-rays

We report the measurement of the energies of the 4f → 3d, 3d → 2p and 2p → 1s atomic transitions in muonic ¹⁸¹Ta. Using transitions to and from the 1s and 2p levels, as well as the hyperfine splittings of the 2p and 3d states, we obtained the radial charge parameters assuming deformed Fermi distributions. We found the intrinsic static quadrupole moment Q₀ = 6.82 ± 0.06 e · b, in excellent agreement with Coulomb excitation results. We verified that the dynamic (corresponding to transitions to the first excited state) and the static (ground state) E2 moments were equal to within 1.1 %. The intrinsic hexadecapole moment was determined to be Π₀ = ?0.12 ± 0.40 e · b².