Extended conjugated mesogens: synthesis and mesomorphic properties of H-shaped mesogens based on 3,3ʹ,5,5ʹ-tetrasubstituted 2,2ʹ-bithiophene with oligo(1,4-phenyleneethynylene) arms

ABSTRACT

A new class of extended conjugated mesogens, namely H-shaped mesogens based on 3,3ʹ,5,5ʹ-tetrasubstituted 2,2ʹ-bithiophene with oligo(1,4-phenyleneethynylene) arms, have been synthesised, and the relationships between molecular structures and mesomorphic properties investigated. Tetraalkyl, tetraalkoxy and dialkyldialkoxy derivatives, [R¹C₆H₄CCC₆H₂(C₂H₅)₂CC]₂[R²C₆H₄CCC₆H₂(C₂H₅)₂CC]₂C₈H₂S₂ where R¹ and R² = alkyl and alkoxy chains of different lengths, exhibit nematic phases. The length, number and position of the terminal chains strongly affect the mesomorphic properties. The tetraalkyl derivatives in which R¹ = R² = pentyl to heptyl exhibit enantiotropic mesophases, whereas the derivatives with octyl or nonyl chains exhibit monotropic mesophases. The tetraalkoxy derivatives in which R¹ = R² = pentyloxy to nonyloxy all exhibit enantiotropic nematic phases. The mesophase range increases with increasing alkoxy chain length, except that the octyloxy and nonyloxy derivatives have almost the same temperature range. The dialkyldialkoxy derivatives in which R¹ = alkyl; R² = alkoxy and in which R¹ = alkoxy; R² = alkyl (R¹ and R² = heptyl, nonyl, hexyloxy or nonyloxy) exhibit enantiotropic mesophases. The derivatives in which R¹ = alkoxy have a significantly lower crystal–nematic transition temperature than the corresponding derivatives (R² = alkoxy), although the two types of derivatives have a similar nematic–isotropic transition temperature.

Graphical Abstract

KEYWORDS:

• Extended conjugated mesogens
• H-shaped mesogens
• 2,2ʹ-bithiophene
• oligo(1,4-phenyleneethynylene)
• structure–property relationship

Acknowledgements

We thank Dr Ritsuko Nagahata and Ms Yuko Saito for carrying out the MALDI–TOF–MS measurements, Ms Shizuko Shibasaki for providing the EA data and Ms Hiroko Kobashi for maintaining the NMR spectrometer.

Disclosure statement

No potential conflict of interest was reported by the authors.

Supplementary material

Supplemental data for this article can be accessed here.

Additional information

Funding

This work was supported by AIST.