Modular Approach to Chromophore Encapsulation in Fluorinated Arylene Vinylene Ether Polymers Possessing Tunable Photoluminescence

Abstract

New fluorinated arylene vinylene ether (FAVE) polymers were prepared by a facile, metal-free condensation polymerization of fluorene, phenylenevinylene, dithiophene, or thiadiazole chromophore-containing bisphenols with bis(trifluorovinyloxy)biphenyl. The addition of chromophores encapsulated into the polymers were prepared in good yields and characterized by 1 H and 19 F NMR and GPC. Thermal analysis by differential scanning calorimetry (DSC) confirmed the polymers are entirely amorphous and are easy to solution process, producing optically transparent, flexible films. Thermal gravimetric analysis (TGA) showed they possess high thermal stability with decomposition temperatures of 340-387°C and 308-443°C in nitrogen and air, respectively. Chromophore inclusion was confirmed by ultraviolet-visible (UV-vis) spectroscopy, which demonstrated tailorable photoluminescence (PL) in both the solution and the solid state by selective substitution of the chromophore. Polymer thin film PL studies revealed notable red-shifts compared with polymer solutions presumably attributable to aggregation in the solid state. Solution quantum yields of the polymers were comparable to those reported for the single chromophores used in this study.

Synthesis of silyl-functionalized oligothiophene-based polymers with bright blue light-emission and high refractive index

“…Therefore, non-conjugated polymer matrixes have been extensively used to either blend or covalently attach single molecules or conjugated segments. Such systems have been shown to minimize undesired fluorescence by excimer and interchain aggregation [9]. In this paper, we report the synthesis of partially conjugated polymers with a silyl-group-substituted oligothiophene and a short alkyl chain in the main chain by hydrosilylation polymerization [10] and describe their optical properties such as luminescence and refractive index.…”

Facile method towards functionalization of partially fluorinated polyarylethers via sequential post-polymerization modification

“…Cs 2 CO 3 and NaH were used as a base to perform polymerization. According to previous studies [10], FAVE polymers usually contain both 1,2-difluoroethylene (CF = CF, mixture of ca. 1.3:1 (Z)/(E)-isomers) and 1,2,2-hydrofluoroethane (CHFCF 2 ) groups on the backbone.…”

“…Functionalized fluoropolymers would be of interest because they would combine the aforementioned merits of fluorinated materials for specific applications [4]. Such tailored fluoropolymers, specifically PFCB aryl ethers, have been involved in various applications including thermally crosslinkable additives [5], proton exchange members (PEMs) for fuel cells [6,7], chemical sensors [8,9], polymer light emitting diodes (PLEDs) [10], gas separation membranes [11], and electro-optical (EO) materials [12,13].…”

“…Although PPM has been widely used to prepare non-fluorinated functional polymers [29][30][31][32][33][34], very few functional fluoropolymers were prepared via PPM [7,[35][36][37][38][39]. Recently a new class of fluoropolymers, partially fluorinated arylene vinylene ether (FAVE) polymers, was developed [5,10]. FAVE polymers be can easily prepared from traditional step-growth polymerization of commercially available bisphenols to bis(trifluorovinyl) aryl ethers (Scheme 1) under low temperatures (around 80°C) and mild reaction conditions (Cs 2 CO 3 as a catalytic base or the salt of biphenols from NaH in DMF) and exhibit excellent solubility in various common organic solvents and excellent chemical resistance (to acids, bases, free radicals, solvents and petroleum).…”

Synthesis, Characterization, and Properties of New Fluorosilicone Block Copolymers

“…The resulting polymers possess 1,2-difluoroethylene (Z = CF=CF) or 1,2,2-hydrofluoroethane (Z = CHFCF 2 ) enchainment depending on the nature of the base. These polymers can be modularly tailored by functionalization of the aryl group (the functional spacer) for applications including thermally crosslinkable fluoroelastomer additives (10,11), proton exchange membranes (PEMs) for hydrogen-based fuel cells (12), polymer light emitting diodes (PLEDs) (13), and chemical sensors (14,15). The work herein entails the expansion of FAVE polymer systems with the first preparation of silicone block PFCB aryl ether copolymers.…”