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.     

Review: Gaile,A.A., Proskuryakov,V.A., Semenov,L.V., Pul'tsin,N.M., Parizheva,N.V., Zakharov,A.P., Apter,Yu.M., and Solodova,N.I., Predel'nye koeffitsienty aktivnosti uglevodorodov: Spravochnik (Limiting Activity Coefficients of Hydrocarbons in Specific Solvents: A Handbook), Gaile,A.A., Ed.

Russian Journal of Applied Chemistry -     

Review: Zainullin,Kh.N., Babkov,V.V., Zakirova,D.M., Chulkov,A.N., and Iksanova,E.M., Utilizatsiya osadkov stochnykh vod gal'vanicheskikh proizvodstv (Utilization of Sediments from Electroplating Shop Wastewater)

Russian Journal of Applied Chemistry -     

ChemInform Abstract: The First Oligomeric Anions of Fluoro-Litho Metallates with Octahedra Sandwich Motive: Cs4K((F3M(III)F3)Li(F3M(III)F3)), M(III): Ga,Fe.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

Review: Beloglazov,I.N., Golubev,V.O., Tikhonov,O.N., Kuukka,J., and Jüaskelüainen,Ed., Fil'trovanie tekhnologicheskikh pul'p (Filtration of Process Pulps)

Russian Journal of Applied Chemistry -     

Review: Blinov,L.N., Khimiko-ekologicheskii slovar'-spravochnik (Chemical-Ecological Dictionary-Reference Book)

Russian Journal of Applied Chemistry -     

Heterobimetallic Clusters of Copper(I) with Trithiotungstate and Trithiomolybdate. Synthesis and Characterization of the Octanuclear Clusters [Et(4)N](4)[M(4)Cu(4)S(12)O(4)] (M = Mo, W) and the Dodecanuclear Clusters [M(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (M = Mo, W; TMEN = N,N,N',N'-Tetramethylethylenediamine)

Synthetic methods for [Et(4)N](4)[W(4)Cu(4)S(12)O(4)] (1), [Et(4)N](4)[Mo(4)Cu(4)S(12)O(4)] (2), [W(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (3), and [Mo(4)Cu(4)S(12)O(4)(CuTMEN)(4)] (4) are described. [Et(4)N](2)[MS(4)], [Et(4)N](2)[MS(2)O(2)], Cu(NO(3))(2).3H(2)O, and KBH(4) (or Et(4)NBH(4)) were used as starting materials for the synthesis of 1 and 2. Compounds 3 and 4 were produced by reaction of [Et(4)N](2)[WOS(3)], Cu(NO(3))(2).3H(2)O, and TMEN and by reaction of [Me(4)N](2)[MO(2)O(2)S(8)], Cu(NO(3))(2).3H(2)O, and TMEN, respectively. Crystal structures of compounds 1-4 were determined. Compounds 1 and 2 crystallized in the monoclinic space group C2/c with a = 14.264(5) ?, b = 32.833(8) ?, c = 14.480(3) ?, beta = 118.66(2) degrees, V = 5950.8(5) ?(3), and Z = 4 for 1 and a = 14.288(5) ?, b = 32.937(10) ?, c = 14.490(3) ?, beta = 118.75(2) degrees, V = 5978.4(7) ?(3), and Z = 4 for 2. Compounds 3 and 4 crystallized in the trigonal space group P3(2)21 with a = 13.836(6) ?, c = 29.81(1) ?, V = 4942(4) ?(3), and Z = 3 for 3 and a = 13.756(9) ?, c = 29.80(2) ?, V = 4885(6) ?(3), and Z = 3 for 4. The cluster cores have approximate C(2v) symmetry. The anions of 1 and 2 may be viewed as consisting of two butterfly-type [CuMOS(3)Cu] fragments bridged by two [MOS(3)](2-) groups. Eight metal atoms in the anions are arranged in an approximate square configuration, with a Cu(4)M(4)S(12) ring structure. Compounds 3 and 4 can be considered to consist of one [M(4)Cu(4)S(12)O(4)](4-) (the anions of 1 and 2) unit capped by Cu(TMEN)(+) groups on each M atom; the Cu(TMEN)(+) groups extend alternately up and down around the Cu(4)M(4) square. The electronic spectra of the compounds are dominated by the internal transitions of the [MOS(3)](2-) moiety. (95)Mo NMR spectral data are investigated and compared with those of other compounds.     

Measurements of the order parameter by proton N.M.R. on N-(4-alkoxybenzylidene)4'-toluidines

N-(4-alkoxybenzylidene)4'-toluidines are a family of organic compounds which present a nematic and (depending on the chain length) a smectic mesophase. We have performed proton spin echo measurements on some members of the family in these mesophases. N.M.R. spectra present well-defined structures that can be assigned to one of the two end methyl groups on the basis of phenomenological as well as analytical discussion, despite the large number of protons contributing to the total line shape. The order parameter derived from this analysis is compared with optical data on the same compounds.     

M1 transition probabilities between fine structure components2L J (L ≥ 1)

Spontaneous emission transition probabilities of the magnetic dipole transitions between states of ground state configurations consisting of onenl electron (or a hole) outside a closed shell have been calculated by using relativistic terms of order α² Z ² and using hydrogenic orbitals to calculate the required overlap integrals. The line strengths calculated for the Boron and Fluorine isoelectronic sequences are in excellent agreement with the calculations involving Dirac wavefunctions for all ions uptoZ=60. The maximum difference at the highest value ofZ=92 is about 6%. Our calculated lifetimes for the state 2p ^{5 2} P _1/2 for Fluorine-like Mg IV and Fe XVIII are 5.03 s and 51.7 µs respectively which are in excellent accord with corresponding values 5.00 s and 51.0 µs calculated by using sophisticated configuration interaction wavefunctions within the Breit-Pauli approximation. Our calculated value of lifetime for Thalium-like Pb II is 40.0 ms which is in good accord with the experimental value of 41.2 ms. New results are presented for the highly ionized ions in the Al-like and Cl-like isoelectronic sequences. The present analysis can be exploited for all the ions in the isoelectronic sequences of elements of groups III A, III B VII A of the periodic table.