Synthesis and liquid crystalline behavior of a series of ferrocene 1,1′-bis-azino-derivatives

A series of liquid-crystalline ferrocene derivatives, Fe{C₅H₄-C(CH₃)=N-N=CH-C₆H₃(X)-OOC-C₆H₄-OC _n H_2n+1}₂ (X = H, OH;n = 3 to 12), were obtained by the condensation of 1,1 -bishydrazondiacetylferrocene withp-alkoxybenzoyloxybenzaldehides. According to DSC and polythermic microscopy, all of the compounds exhibit an enantiotropic nematic mesophase in the 150–230 °C temperature range. A polycrystalline transition precedes the nematic transition. The liquid crystalline properties of the obtained compounds were investigated with respect to the number of carbon atoms in the terminal alkyl chain and the terminal hydroxyl group. The composition and structure of the obtained compounds were determined by elemental analysis and IR and NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 358–361, February, 1995.This work was carried out with financial support from the Russian Fundation for Basic Research (Project No. 94-03-08978).     

Synthesis, computational modelling and liquid crystalline properties of some [3]ferrocenophane-containing Schiff’s bases and β-aminovinylketone: Molecular geometry-phase behaviour relationship

Rotationally fixed [3]ferrocenophane extends the variety of possible molecular geometries in its derivatives in comparison with unbridged ferrocenes. In this respect molecular geometry-liquid crystalline properties relationship studies in [3]ferrocenophane mesogens are of considerable interest. Different positional isomers of mono- and di-substituted [3]ferrocenophanes which are obtained by incorporating one or two promesogenic building blocks into the cyclopentadienyl rings are reported in this article. A series of mono-substituted [3]ferrocenophane-containing Schiff’s bases was synthesized by condensing isomeric p-aminophenyl [3]ferrocenophanes with appropriate aldehydes. Isomers of di-substituted [3]ferrocenophane amines gave rise to a series of azomethines with two promesogenic substituents in the cyclopentadienyl rings. Besides, a β-enaminoketone was prepared from 3-(p-aminophenyl)[3]ferrocenophane. Nematic and smectic mesophases were observed in the synthesized compounds under a polarizing optical microscope. The [3]ferrocenophane-containing β-enaminoketone showed complex mesomorphic behaviour connected with occurrence of the keto-enamine and imino-enol tautomeric equilibrium in this compound. On the base of computational models obtained by semi-empirical quantum chemistry calculations the molecular geometry-phase behaviour relationships were examined. It was demonstrated that mesomorphism of [3]ferocenophane azomethines depends on the spatial orientation of the substituents with respect to the propanediyl bridge in a case of mono-, and as well as to each other in a case of di-substituted derivatives.     

The synthesis of liquid crystalline lanthanide complexes and their magnetic birefringence

Liquid crystalline complexes of the type [ML(LH)₂](NO₃)₂, where LH=C₇H₁₅O-C₆H₃(OH)CH=N-C₁₈H₃₇ and M=Gd, Dy, and La, have been obtained. All of them exhibit the S_A phase and have high magnetic birefringence constants due to the association of the complexes in solution. In the case of the dysprosium derivative, the effect is much stronger (four orders of magnitude greater than the usual value) because of the high magnetic anisotropy of the particles of the complex.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1003–1005, June, 1994.The authors are grateful to Prof. S. G. Vul'fson for helpful advice and discussions.     

Exchange interaction mechanisms in 1,3,5,7-tetramethyl-2,6-diazaadamantane <Emphasis Type="Italic">N,N’</Emphasis>-dioxyl biradical

The exchange interaction parameters were calculated and the spin density distribution over the organic skeleton of the 1,3,5,7-tetramethyl-2,6-diazaadamantane N,N’-dioxyl biradical was studied based on the results of quantum chemical modeling of the biradical structure by the DFT method using various hybrid functionals (UB3LYP, LC-wPBE, UCAM-B3LYP, UHSEH1PBE) with the 6-311++G(2d,2p) basis set and by the UHF method with the same basis set. The characteristics of the direct orbital overlap between the N atoms of the two nitroxide groups were determined. The values of the J constant, obtained using different calculation methods, were found to be similar to each other. It was established that there is ferromagnetic exchange interaction between the radical sites in the system in question, which occurs predominantly according to the spin polarization mechanism in the 2,6-diazaadamantane core, and the various spin density transfer pathways through the C atoms of the organic skeleton were found to be nonequivalent. The direct overlap of the upper singly-occupied МОs with localization on the nitroxide groups led to a noticeable additional contribution of the antiferromagnetic exchange interaction. Despite the latter factor, the total contribution of these two mechanisms (spin polarization and direct through-space exchange) resulted in the triplet ground state in the biradical studied.     

Synthesis and liquid crystal properties of copper(II) and palladium(II) chelates with new ferrocene-containing enaminoketones

Heterometallic liquid crystals are of special interest because of the possibility to combine optical, magnetic and electric properties of different metal ions in one mesogenic molecule. In order to investigate new heteropolynuclear mesogenic systems, a series of β-aminovinylketone ligands derived from acetyl ferrocene have been synthesized. Subsequently Cu(II) and Pd(II) ions were incorporated into the enaminoketone chelate core. The obtained ligands and complexes were characterized by element analysis, ¹H NMR, IR and UV–Vis spectroscopies. According to thermal polarizing microscopy and DSC studies, the ligands and Cu(II) complexes exhibit disordered soft crystal phases upon cooling from the isotropic liquid state. The Pd(II) complexes showed monotropic smectic C mesomorphism. The metal centres in the synthesized heteropolynuclear mesogens are in close vicinity to each other, which is of considerable interest from the viewpoint of the potential electron-transfer interactions between a ferrocene core and the central ions.     

Syntheses and structural characterization of some mono- and di-p-nitrophenyl[3]ferrocenophanes: X-ray structure of [3]ferrocenophane, 3-p-nitrophenyl[3]ferrocenophane, and 3,4′-bis-(p-nitrophenyl)[3]ferrocenophane; DFT calculations on ferrocene derivatives

[3]Ferrocenophane (3a) reacts in a Gomberg reaction with diazotized p-nitroaniline to give a mixture of mono- and di-substituted products. The isomeric pairs of 3- and 2-(p-nitrophenyl)[3]ferrocenophanes (4 and 5), as well as 3,4′- and 3,4-bis-(p-nitrophenyl)[3]ferrocenophanes (6 and 7) were separated from the mixture by column chromatography on Al₂O₃ and characterized by means of mass, IR, UV, ¹H-NMR spectroscopy, and by X-ray analysis (4 and 6). PM3/tm and density functional theoretical calculations on ferrocene (1) and ferrocenophane derivatives are reported. A refined X-ray structure determination of [3]ferrocenophane (3a) is given.     

Liquid-crystalline CuII and PdII complexes with nonmesogenic ferrocene-containing β-aminovinyl ketone

New liquid-crystalline heteropolynuclear complexes L₂M (M=Cu²⁺ (2a), Pd²⁺ (2b)) were synthesized by the reactions of C₅H₅FeC₅H₄−C₆H₄NH−C₂H₂−(CO)−C₆H₄OC₁₂H₂₅ (1, LH) with copper(ii) and palladium(ii) acetates. Compound2b was found to possess monotropic nematic and smectic phases;2a exhibits the monotropic nematic phase and a phenomenon of “double melting”. The compositions and structures of compounds1 and2a,b were established by elemental analysis,¹H and¹³C NMR, ESR, and IR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 381–383, February, 1999.     

Phase behavior of some mono-substituted ferrocene- and [3]ferrocenophane-containing nematics with the cyclohexane ring in the rigid core

Generally, incorporation of the cyclohexane rings into the rigid core of rod-like mesogens leads to improved technological parameters, i.e. low viscosity, ambient transition temperatures and stability of the nematic state. Taking this into consideration, a series of novel cyclohexane-containing derivatives of ferrocene has been synthesized. The effect of various structural factors on liquid crystalline behavior of the synthesized ferrocene-containing nematics has been examined. Ferrocenophane compounds exhibited enhanced liquid crystalline properties in comparison with the derivatives of unbridged ferrocene. Depending on thermal prehistory of the samples, some of the synthesized ferrocenomesogens showed remarkable migration of the phase transition temperatures. In one case such behavior led to stabilization of the initially monotropic nematic mesophase in subsequent heating cycles. In another case, the phase transition shifts caused the lowering of the crystal-to-nematic transition temperature and the broadening of the mesophase range. There was also a case of alteration from the initially enantiotropic to monotropic behavior. The obtained novel metallomesogens are important footsteps toward the development of low-viscous and low-temperature materials for liquid crystal applications possessing a chromophoric, redox-switchable, polarizable and chemically stable superaromatic ferrocene unit.     

Liquid crystal phases generated by supramolecular self-assembly of biforked amphiphilic imidazoles

Functional groups with the capability of hydrogen bonding are widely used in the molecular design and preparation of liquid crystalline supramolecular systems, a rapidly growing area of materials showing a high sensitivity towards external stimuli. A series of novel imidazole-containing Schiff's bases replenishing the family of supramolecular liquid crystals has been synthesised and characterised by proton nuclear magnetic resonance, Fourier transform infrared, and ultraviolet–visible spectroscopy, and elemental analyses. Variation of lengths of the terminal alkyl substituents in the obtained amphiphilic imidazoles within 6, 8, 10, 12, 14 and 16 carbon atoms leads to significant changes in their thermal behaviour, micro-segregation and supramolecular self-assembly. Lower homologues were non-mesomorphic, while intermediate members of the homologous series exhibited monotropic bilayered smectic and columnar mesophases. A higher homologue with 16 carbon atoms has an increased trend towards crystallisation of the aliphatic chains and did not exhibit mesomorphism again. The liquid crystalline mesophases were identified and investigated by polarised optical microscopy, differential scanning calorimetry, X-ray diffraction and thermal emission microscopy methods. According to X-ray diffraction characteristics, the smectic mesophase has a bilayered structure where the hydrophilic imidazole groups form a continuous hydrogen bonded network. The interface curvature created by the second alkyl chain leads to the appearance of columnar nanostructures in homologues with 12 and 14 aliphatic carbon atoms.