High-Temperature Chromophores and Perfluorocyclobutyl Copolymers for Electro-optic Applications

Abstract

The synthesis and hyperpolarizabilities of a series of push−pull chromophores containing a bis-(4-methoxyphenyl) amine donor and efficient acceptor bridges with thiophene and ring-locked polyene are presented. The chromophores are readily soluble in common organic solvents and exhibit high thermal decomposition temperatures (highest T d was 358 °C). Molecular hyperpolarizabilities (β) of the chromophores were measured by hyper-Raleigh scattering at 1604 nm (highest β was 20 000 × 10−30 esu). The electrochemical behavior of the chromophores was studied by cyclic voltammetry and agreed well with the observed intrinsic nonlinearities. In addition, preliminary results of conjugated polyene chromophores containing aryl trifluorovinyl ether monomers were synthesized and copolymerized via thermal cyclodimerization, affording perfluorocyclobutyl aryl ether polymers with high glass transitions (highest T g was 224 °C) and a good thermal stability (typical T d was >350 °C). These chromophores can be used to develop electro-optic materials due to their large optical nonlinearities, good absorption characteristics, high thermal stability, and excellent solubility with organic solvents and polymeric materials.

Triarylamine-enchained semifluorinated perfluorocycloalkenyl (PFCA) aryl ether polymers

“…chromophorization-synthesizing an electro-optic (EO) chromophore incorporated aldehyde (P4) can be further modified into a range of application-specific molecules, including extension into an EO chromophore, hole-transport and photovoltaic materials [29,34,36,37]. EAS reaction on these PFCP aryl ether polymers demonstrates the accessibility of these TAA moieties for further post polymerization modifications, which extends the overall versatility of this polymeric system.…”

“…In this manuscript, we are presenting new per- [28] fluorocycloalkenyl (PFCA) aryl ether polymers with triarylamine moieties, and cross-linking behavior of PFCA aryl ether polymers. TAA moieties provide an excellent reaction site for post polymerization modification to make these fluoropolymers application specific [26,29].…”

Theory-Guided Design of Organic Electro-Optic Materials and Devices

“…Initial research into lattice hardening by crosslinking involved exploitation of free radical and condensation reactions [7]. More recently, these protocols have been replaced by lattice hardening based on utilization of cycloaddition reactions including those involving the fluorovinyl ether moiety [16][17][18] and Diels-Alder/Retro-Diels-Alder reactions [16,[19][20][21]. The latter class of reactions has been particularly successful in yielding final material glass transition temperatures as high as 300 °C [16,[19][20][21].…”

Thermally Polymerized Rylene Nanoparticles

“…10 Moreover, due to the availability of a key synthetic intermediate ( 1 , Figure 1B), the straight-forward incorporation of phenyl TFVE moieties into a variety of chromophore skeletons is possible. 11 In the past decade, TFVE-containing chromophore thermosets have been explored as thermally-stable nonlinear optical polymers, 12 optical waveguides 13 and hole-transporting materials in organic light emitting diodes. 14 …”