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A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (1H), and fluorine 19 (19F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (Mns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12–1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60–80% solvent fraction. A lyotropic smectic phase contains 10 nm polymer platelets connected by tie molecules. The structure also incorporates a square packing motif within platelets. Thermal properties of polymers were affected by the size of counterions as determined by differential scanning calorimetry and thermogravimetric analysis measurements. Their ultraviolet-visible (UV-Vis) absorption spectra in different organic solvents were essentially identical, indicating that the closely spaced π-π* transitions occurred in their conjugated polymer structures. In contrast, the emission spectra of polymers exhibited a positive solvatochromism on changing the polarity of solvents. They emitted green lights in both polar and nonpolar organic solvents and showed blue light in the film-states, but their λem peaks were dependent on the size of the counterions. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), and their λem peaks were blue shifted.

Dynamic casting of conjugated polymer films on liquid-substrate is a unique method which provides thin floating-film and can be easily transferred on a desired substrate by stamping. The important feature in this procedure is associated with the formation of thin polymeric film during compression and solidification controlled by viscous drag of liquid substrate and solvent evaporation of the polymer, respectively. Lyotropic liquid-crystalline (LC) characteristics of conjugated polymer possibly assist to orient the polymer chain in one direction. It is found that this method produce highly oriented thin films (dichroic ratio > 5) of thiophene-based conjugated polymers such as PBTTT-C14, PQT-C12 and non-regiocontrolled poly(3-hexylthiophene) NR-P3HT. On the other hand, weak orientation intensity in regioregular poly(3-hexylthiophene) RR-P3HT was found. The mechanism for this diverse orientation in thiophene-based conjugated polymers is discussed in correlation with the backbone chemical structure and lyotropic LC phase transition during the floating-film formation. [ABSTRACT FROM AUTHOR]

It was demonstrated experimentally that the vapors of a mesophase-generating solvent, i.e., a solvent forming a lyotropic liquid-crystalline phase with a polymer, changed the spatial structure and optical density of natural polysaccharides (cellulose acetates). In this process, the value of specific optical rotation of the polymer modified by the vapors varied in a wide range up to sign inversion. The action of vapors on the polymer follows a peculiar dose-effect pattern, with lower doses producing a stronger effect. Application of this approach to the study into specific structural characteristics of biopolymers, such as DNA, is proposed. [ABSTRACT FROM AUTHOR]

A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (1H), and fluorine 19 (19F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (Mns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12–1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60–80% solvent fraction. A lyotropic smectic phase contains 10 nm polymer platelets connected by tie molecules. The structure also incorporates a square packing motif within platelets. Thermal properties of polymers were affected by the size of counterions as determined by differential scanning calorimetry and thermogravimetric analysis measurements. Their ultraviolet-visible (UV-Vis) absorption spectra in different organic solvents were essentially identical, indicating that the closely spaced π-π* transitions occurred in their conjugated polymer structures. In contrast, the emission spectra of polymers exhibited a positive solvatochromism on changing the polarity of solvents. They emitted green lights in both polar and nonpolar organic solvents and showed blue light in the film-states, but their λem peaks were dependent on the size of the counterions. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), and their λem peaks were blue shifted. [ABSTRACT FROM AUTHOR]