Synthesis and magnetic properties of liquid crystalline lanthanide complexes with alkylsulfate counterions

The reaction of Schiff"s base L with lanthanide alkylsulfates affords liquid crystalline complexes with the general formula L₃Ln(C_nH_2n+1OSO₃)₃. The liquid crystalline structure and magnetic properties are studied by polarization thermal microscopy, differential scanning calorimetry, X-ray diffraction, and measurement of magnetic susceptibility. The temperatures of the existence of the mesophase and magnetic anisotropy of the complexes with the same lanthanide depend on the chain length of the alkyl fragment in the sulfate anion.     

The even–odd effect in the dependence of optical anisotropy on the number of protons in complexing agent ions of liquid-crystal coordination compounds of lanthanides

The values of optical anisotropy of two series of thermotropic nematic liquid crystalline complexes based on the ions Eu⁺³, Gd⁺³, Tb⁺³, and Dy⁺³ have been determined. Even–odd alternation of optical anisotropy with an increasing number of protons in ions of lanthanides has been observed. It is established that, in the considered series of lanthanidomesogens, optical anisotropy is more sensitive to changes in the ligand structure of complexes than to the variation of the complexing agent.     

The influence of a complexing agent ion on the magnitude of the optical anisotropy of lanthanidomesogens

Measurements of the refractive indices and optical anisotropy of a series of liquid crystalline coordination compounds based on lanthanides with an identical ligand environment have been carried out. It was found that the magnitude of the optical anisotropy of the investigated complexes was several times smaller than the anisotropy of organic liquid crystals. Analysis of the results showed that the variation of the ion complexing agent had little effect on the magnitude of the optical anisotropy in the mesogenic complexes containing the same ligands. The even-odd alternation of the optical anisotropy of lanthanidomesogens at the increasing the number of protons in the ions of the lanthanides has been observed.

     

Phase behaviour,structural properties and intermolecular interactions of systems based on substituted thiacalix[4]arene and nonionic surfactants

Supramolecular organised materials were prepared from nonionic surfactants and the following macrocyclic ionic liquids: n-tert-butylthiacalix[4]arenes containing quaternary ammonium fragments with amino acid substituents. Tetraethylene glycol monododecyl ether and decadiethylene glycol monododecyl ether were used as nonionic surfactants. They form lamellar and hexagonal mesophases in aqueous media, respectively. Liquid crystal and structural properties of these systems were studied. Intermolecular interactions of system components leading to formation of lyomesophases were estimated. Molecular structure of thiacalixarene contributes to the formation of a hydrogen bonding with surfactants. This process, in turn, initiates formation of a denser packed hexagonal structure.     

Does the solid-liquid crystal phase transition provoke the spin-state change in spin-crossover metallomesogens?

Three types of interplay/synergy between spin-crossover (SCO) and liquid crystalline (LC) phase transitions can be predicted: (i) systems with coupled phase transitions, where the structural changes associated to the Cr<-->LC phase transition drives the spin-state transition, (ii) systems where both transitions coexist in the same temperature region but are not coupled, and (iii) systems with uncoupled phase transitions. Here we present a new family of Fe(II) metallomesogens based on the ligand tris[3-aza-4-((5-C(n))(6-R)(2-pyridyl))but-3-enyl]amine, with C(n) = hexyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, R = hydrogen or methyl (C(n)-trenH or C(n)-trenMe), which affords examples of systems of types i, ii, and iii. Self-assembly of the ligands C(n)-trenH and C(n)-trenMe with Fe(A)2 x xH2O salts have afforded a family of complexes with general formula [Fe(C(n)-trenR)](A)2 x sH2O (s > or = 0), with A = ClO4(-), F-, Cl-, Br- and I-. Single-crystal X-ray diffraction measurements have been performed on two derivatives of this family, named as [Fe(C6-trenH)](ClO4)2 (C(6)-1) and [Fe(C6-trenMe)](ClO4)2 (C(6)-2), at 150 K for C(6)-1 and at 90 and 298 K for C(6)-2. At 150 K, C(6)-1 displays the triclinic space group P, whereas at 90 and at 298 K C(6)-2 adopts the monoclinic P2(1)/c space group. In both compounds the iron atoms adopt a pseudo-octahedral symmetry and are surrounded by six nitrogen atoms belonging to imino groups and pyridines of the ligands C(n)-trenH and C(n)-trenMe. The average Fe(II)-N bonds (1.963(2) A) at 150 K denote that C(6)-1 is in the low-spin (LS) state. For C(6)-2 the average Fe(II)-N bonds (2.007(1) A) at 90 K are characteristic of the LS state, while at 298 K they are typical for the high-spin (HS) state (2.234(3) A). Compound C(6)-1 and [Fe(C18-trenH)](ClO4)2 (C(18)-1) adopts the LS state in the temperature region between 10 and 400 K, while compound C(6)-2 and [Fe(Cn-trenMe)](ClO4)2 (n = 12 (C(12)-2), 18 (C(18)-2)) exhibit spin crossover behavior at T(1/2) centered around 140 K. The thermal spin transition is accompanied by a pronounced change of color from dark red (LS) to orange (HS). The light-induced excited spin state trapping (LIESST) effect has been investigated in compounds C(6)-2, C(12)-2 and C(18)-2. The T(1/2)LIESST is 56 K (C(6)-2), 48 K (C(16)-2), and 56 K (C(18)-2). On the basis of differential scanning calorimetry, optical polarizing microscopy, and X-ray diffraction findings for C(18)-1, C(12)-2, and C(18)-2 at high temperature a smectic mesophase SX has been identified with layered structures similar to C(6)-1 and C(6)-2. The compounds [Fe(C(n)-trenH)](Cl)2 x sH2O (n = 16 (C(16)-3, s = 3.5, C(16)-4, s = 0.5, C(16)-5, s = 0), 18 (C(18)-3, s = 3.5, C(18)-4, s = 0.5, C(18)-5, s = 0), 20 (C(20)-3, s = 3.5, C(20)-4, s = 0.5, C(20)-5, s = 0)) and [Fe(C18-tren)](F)2 x sH2O (C(18)-6, s = 3.5, C(18)-7, s = 0) show a very particular spin-state change, while [Fe(C18-tren)](Br)2 x 3H2O (C(18)-8) together with [Fe(C18-tren)](I)2 (C(18)-9) are in the LS state (10-400 K) and present mesomorphic behavior like that observed for the complexes C(18)-1, C(12)-2, and C(18)-2. In compounds C(n)-3 50% of the Fe(II) ions undergo spin-state change at T(1/2) = 375 K induced by releasing water, and in partially dehydrated compounds (s = 0.5) the Cr-->SA phase transition occurs at 287 K (C(16)-4), 301 K (C(18)-4) and 330 K (C(20)-4). For the fully dehydrated materials C(n)-5 50% of the Fe(II) ions are in the HS state and show paramagnetic behavior between 10 and 400 K. In the partially dehydrated C(n)-4 the spin transition is induced by the change of the aggregate state of matter (solid<-->liquid crystal). For compound C(18)-6 the full dehydration to C(18)-7 provokes the spin-state change of nearly 50% of the Fe(II) ions. The compounds C(n)-3 and C(18)-6 are dark purple in the LS state and become light purple-brown when 50% of the Fe(II) atoms are in the HS state.     

Effect of Metal Complex Binding on the Properties of Polymethyl Methacrylate

Coordination binding of polymethyl methacrylate with copper(II) ions was studied by IR spectroscopy and viscometry.     

Paramagnetic Mn:CdS/ZnS quantum dots: synthesis,luminescence, and magnetic properties

Russian Chemical Bulletin -     

Crystal and molecular structures of diphenylethylarsine sulfide,C14H15AsS,and p-tolyldiethylarsine sulfide,C11H17AsS

In order to elucidate the influence of aryl or alkyl substituents on the nature of the ? bond, which controls the complexing properties of the substances (Alk)n(Ar)_3-nAsS (n = 0–3), the X-ray investigation of (p-MeC₆H₄)Et₃AsS (TDEAS) and Ph₂EtAsS (DPEAS) has been carried out. It was shown that the bond length AsS in these compounds has intermediate values (2.0896 and 2.0812 Å) in respect to those previously found by us in Et₃AsS and Ph₃AsS (2.115 and 2.077 Å). This confirms the conclusion that the increase of the number of aryl substituents in tertiary arsine sulfides leads to a decrease of electron density on the As atom along with simultaneous strengthening of the π-interaction between As and S.     

Synthesis and liquid-crystalline properties of 4-(heptyloxy)-n-(aryl)benzaldimin-2-ols

The synthesis and liquid-crystalline properties of 4-(heptyloxy)-N-(aryl)benzaldimin-2-ols have been described. The compounds obtained have smectic and nematic mesomorphism. Alternation of the bleaching temperatures (T_bl) with variation of the length of the alkyl radical in the N-aryl fragment has been noted. The dependence of T_bl on the contribution of the substituent to the polarizability of the molecule ² is expressed by the equation T_bl=9.7+1.7².Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1997–2001, September, 1989.     

Spin-crossover and liquid crystal properties in 2D cyanide-bridged Fe(II)-M(I/II) metalorganic frameworks

Novel two-dimensional heterometallic Fe(II)-M(Ni(II), Pd(II), Pt(II), Ag(I), and Au(I)) cyanide-bridged metalorganic frameworks exhibiting spin-crossover and liquid crystal properties, formulated as {FeL(2)[M(I/II)(CN)(x)](y)}·sH(2)O, where L are the ligands 4-(4-alkoxyphenyl)pyridine, 4-(3,4-dialkoxyphenyl)pyridine, and 4-(3,4,5-trisalkoxyphenyl)pyridine, have been synthesized and characterized. The physical characterization has been carried out by means of EXAFS, X-ray powder diffraction, magnetic susceptibility, differential scanning measurements, and Mo?ssbauer spectroscopy. The 2D Fe(II) metallomesogens undergo incomplete and continuous thermally induced spin transition at T(1/2) ≈ 170 K and crystal-to-smectic transition above 370 K.