Highly refractive, thermostable, and transparent poly(phenylene sulfide) (PPS) derivatives partially including S=O bonds were reported. The polymers were prepared via m-chloroperbenzoic acid (mCPBA) oxidation of the corresponding PPS derivatives, affording...

High-refractive-index polymers (HRIPs) are attractive materials for the development of optical devices with high performances. However, because practical components and structures for HRIPs are limited from the viewpoint of synthetic techniques, it has proved difficult using traditional strategies to enhance the refractive index (RI) of HRIPs to more than a certain degree (over 1.8) while maintaining their visible transparency. Here, we found that poly(phenylene sulfide) (PPS) derivatives featuring both methylthio and hydroxy groups can simultaneously exhibit balanced properties of an ultrahigh RI of n D = 1.85 and Abbe number of ν D = 20 owing to the synergistic effect of high molar refraction and dense intermolecular hydrogen bonds (H-bonds). This brand new strategy is anticipated to contribute to the development of HRIPs displaying ultrahigh RI with adequate Abbe numbers beyond the empirical n D −ν D threshold, which has not been achieved to date.

Dihydroxy-substituted poly(phenylene sulfide) (DOHPPS) was synthesized via oxidative polymerization of bis(2,6-dimethoxyphenyl) disulfide and subsequent deprotection. The synergistic effect of multiple-hydrogen-bond cross-links and the rigidity of the thiophenylene backbone afforded dense yet amorphous supramolecular networks, resulting in a polymer with visible transparency and an ultrahigh refractive index (n D = 1.85).