Ferrocene derivatives structural properties

The thermal characteristics exhibited by the series 11 [18] and 14 [20] proved that interesting liquid crystal properties can be obtained with symmetrically 1,T-disubstituted ferrocene derivatives. The structure of the organic unit, which is combined with the ferrocenyl moiety, must be carefully chosen. 

Ferrocene derivatives 15 exhibited remarkable liquid crystal properties (Fig. 9-13). Indeed, they all gave rise to enantiotropic mesophases. Structures with n = 1 to 11 showed nematic phases. From n = 12 a smectic C phase formed. The latter was monotropic only for 15 (n = 12). The smectic C domain increased from n = 13 to n = 16, and, inversely, the nematic range narrowed. The last member of this series (n = 18) presented one smectic C phase between 159 °C and 179 °C. A nematic to smectic C transition and a focal-conic texture of a smectic C phase are presented in Figs. 9-14 and 9-15, respectively. 

We designed and studied [27] a family of unsymmetrically l,l -disubstituted ferrocene derivatives obtained by combining the organic units A and B (above), used to prepare the families 13 and 14, respectively within the same molecular framework. Structures 25 (Fig. 9-21) led to remarkable mesomorphic properties. All derivatives exhibited liquid crystal properties. Compound 25 (n = 11) gave rise to an enantiotropic smectic A phase. Complex 25 (n = 12) showed an enantiotropic... 

After our investigations on low molar mass ferrocene derivatives, we examined the thermal properties of isomeric polymeric structures. 

The section commences with monosubstituted ferrocene derivatives, after which the influence of the substitution pattern on the formation and stability of liquid-crystalline phases for disub-stituted ferrocene derivatives will be discussed. Next, the influence of the three-dimensional structure of ferrocene on the mesomorphic properties will be highlighted, optically active ferrocene materials will be described and, finally, ferrocene-containing liquid-crystalline dendrimers will be introduced ferrocene-containing liquid-crystalline polymers will not be reported. Note that a review devoted to ferrocene-containing thermotropic liquid crystals has already been published. ... 

ScHLOGL and co-workers [80] have employed TLC on both analytical and preparative scale in their extensive work on syntheses and properties of ferrocene derivatives. It has been used in investigations like following chemical changes, such as oxidations [81] checking the purity of products of synthesis or separating isomers [21, 84]. TLC has further enabled compound classes such as the alkyl ferrocenes to be separated from acyl ferrocenes [82] and correlations between molecular structure and... 

The molecular structure of decabenzylferrocene also helped to explain the rather low solubility of this compound in toluene or benzene, in sharp contrast with the previously found excellent solubility properties of other decabenzylmetallocenes and the pentabenzyl-Cp thallium and indium complexes in these solvents. The steric crowding of the benzyl groups in the ferrocene and their limited mobility leave little space for the solvent arene molecules to interact and subsequently to dissolve the molecule. This is quite similar to the situation encountered in the pentaphenylcyclopenta-dienyl derivatives with their closely packed phenyl rings (see Fig. 3). 

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