The reaction mechanisms for the reactions of cobaltacyclopentadiene with isocyanate and isothiocyanate exclusively in singlet or triplet states, or involving transition between states, were studied by means of hybrid density functional theory (B3LYP) calculations. The results clearly showed that a two-state mechanism involving both singlet and triplet states is more favorable than the corresponding singlestate mechanism for all the reactions. We also found that the reactions of isocyanate and isothiocyanate to give pyridin-2(1H)-one and pyridine-2(1H)-thione complexes, respectively, are more favorable than those that give 2H-pyran-2-imine and 2H-thiopyran-2-imine complexes. This is mainly due to the greater stabilities of pyridin-2(1H)-one and pyridine-2(1H)-thione compared with 2H-pyran-2-imine and 2H-thiopyran-2-imine. A change in spin state plays a crucial role in the two-state mechanism; first, the C]N bond of the isocyanate or isothiocyanate inserts into the CoeCa bond of cobaltacyclopentadiene in the singlet state to give azacobaltacycloheptadienone or azacobaltacycloheptadienethione intermediates, and subsequent reductive elimination in the triplet state gives the pyridin-2(1H)-one or pyridine-2(1H)-thione complex, respectively.

A new homologous series of thermally stable thermotropic liquid crystalline poly(arylidene-ether)s based on 4-tertiary-butyl-cyclohexanone moiety was synthesised by solution polycondensation of 4,4 -diformyl- α , ω -diphenoxyalkanes, I a–f ,or4,4 -diformyl-2,2 -dimethoxy- α , ω -diphenoxyalkanes, II a–f , with the 4-tertiary-butyl-cyclohexanone monomer. A model compound III was synthesised from the monomer with benzaldehyde and characterised by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range of 0.18–0.92 dL/g. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by differential scanning calorimetry (DSC) and optical polarising microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermal properties of those polymers were evaluated by thermogravimetric analysis and DSC measurements and correlated to their structural units. X-ray analysis showed that polymers having some degree of crystallinity in the region 2 θ = 5–60 ◦ . In addition, the morphological properties of selected examples were tested by scanning electron microscopy.

A new homologous series of thermally stable thermotropic liquid crystalline poly(arylidene-ether)s based on 4-tertiary-butyl-cyclohexanone moiety was synthesised by solution polycondensation of 4,4 -diformyl- α , ω -diphenoxyalkanes, I a–f ,or4,4 -diformyl-2,2 -dimethoxy- α , ω -diphenoxyalkanes, II a–f , with the 4-tertiary-butyl-cyclohexanone monomer. A model compound III was synthesised from the monomer with benzaldehyde and characterised by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range of 0.18–0.92 dL/g. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by differential scanning calorimetry (DSC) and optical polarising microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermal properties of those polymers were evaluated by thermogravimetric analysis and DSC measurements and correlated to their structural units. X-ray analysis showed that polymers having some degree of crystallinity in the region 2 θ = 5–60 ◦ . In addition, the morphological properties of selected examples were tested by scanning electron microscopy.