Search

π-Conjugated poly(arylene ethynylene)s containing both thiophene-2,5-diyl and fused metallacycles units in their alternating sequence were synthesized and their optoelectronic features were studied by the UV-vis spectra.

Novel high-refractive-index materials consisting of poly(thiophosphonate)s were developed by the polycondensation of phenylthiophosphonic dichloride with various bisphenols. These polymers exhibit excellent thermal stability (Td5 > 420 °C), moderate to high glass transition temperatures (117–204 °C) and high transparency in the visible light region. Furthermore, they achieve high refractive indices of 1.626–1.687 owing to the highly polarizable sulfur and phosphorous atoms in their backbones and relatively high Abbe numbers of 21.3–27.5.

The birefringent properties of poly(phosphonate)s and poly(thiophosphonate)s possessing various bisphenol structures were investigated. The CR values (orientational birefringence) of the poly(phosphonate)s and the poly(thiophosphonate)s range from −0.3 × 10−9 to + 1.3 × 10−9 Pa−1 and from −0.6 × 10−9 to + 0.8 × 10−9 Pa−1, respectively, which are lower than those of the corresponding bisphenol A-based polymers. The CD values (photoelastic birefringence), which range from + 4.0 × 10−11 to + 4.9 × 10−11 Pa−1, are also lower than those of the corresponding bisphenol A-based polymers. The birefringent properties of poly(phosphonate)s and poly(thiophosphonate)s possessing various bisphenol structures were investigated. The CR values (orientational birefringence) of the poly(phosphonate)s and the poly(thiophosphonate)s range from −0.3 × 10−9 to + 1.3 × 10−9 Pa−1 and from −0.6 × 10−9 to + 0.8 × 10−9 Pa−1, respectively, which are lower than those of the corresponding bisphenol A-based polymers. The CD values (photoelastic birefringence), which range from + 4.0 × 10−11 to + 4.9 × 10−11 Pa−1, are also lower than those of the corresponding bisphenol A-based polymers.

The birefringent properties of bisphenol A-based poly(phosphonate) and poly(thiophosphonate) were investigated. The orientational birefringences (CR values) of the poly(phosphonate) derivatives are in the range from +1.2 × 10–9 to +1.5 × 10–9 Pa–1, which are less than half of those of the conventional bisphenol A-based polymers. In addition, their photoelastic birefringences (CD values) are in the range from +5.7 × 10–11 to +6.1 × 10–11 Pa–1, which are also lower than those of the conventional bisphenol A-based polymers. From the DFT calculations of the polarizability anisotropies of the model compounds, the low birefringent properties of the poly(phosphonate) derivatives are most probably due to the presence of the P═O and P═S groups and the phenyl substituents perpendicularly oriented to the main chain direction.

Poly(arylene ether phosphine oxide)s and poly(arylene ether phosphine sulfide)s with high refractive indices and low birefringences have been developed. The poly(arylene ether phosphine oxide)s were synthesized by the polycondensation of bis(4-fluorophenyl)phenylphosphine oxide with various bisphenols. Subsequently, the poly(arylene ether phosphine sulfide)s were synthesized by the sulfurization reaction of the poly(arylene ether phosphine oxide)s with Lawesson's reagent. These polymers have excellent thermal stabilities (Td5 > 490 °C), high glass transition temperatures (Tg = 198–281 °C), and no absorption in the visible light region. In addition, they achieve high refractive indices of 1.649–1.675 for the poly(arylene ether phosphine oxide)s and 1.671–1.691 for the poly(arylene ether phosphine sulfide)s owing to the highly polarizable P X (X = O, S) groups in their backbones. Their orientational birefringences (CR values) are in the range from +0.7 × 10−9 to +3.0 × 10−9 Pa−1, which are lower than those of the conventional poly(arylene ether ketone) and poly(arylene ether sulfone) (+7.8 × 10−9 and +4.0 × 10−9 Pa−1, respectively).

Herein, we describe the synthesis and chiroptical properties of through-space conjugated polymers with enantiopure planar chiral (R)- and (S)-pseudo-ortho-disubstituted [2.2]paracyclophane skeletons. The polymers exhibited intense circularly polarized luminescence in dilute solutions due to their conformationally stable planar chiral zigzag structures.

We describe the practical optical resolution of rac-pseudo-ortho-dibromo[2.2]paracyclophane to obtain the parent compound for a variety of cyclophane-based planar chiral compounds such as enantiopu...