Facile Synthesis of Thienopyrroledione-Based π-Conjugated Polymers via Direct Arylation Polycondensation under Aerobic Conditions

Abstract

An exploration of the tolerance of a Pd-catalyzed direct arylation polycondensation under aerobic conditions was carried out. The polycondensation of 5-(2-ethylhexyl)thieno-[3,4-c]-pyrrole-4,6dione with 2,7-dibromo-9,9-dioctylfluorene was accomplished smoothly in air by refluxing the solvents, without the need for additional catalysts or additives. This simple modification allowed the use of commercially available reagent-grade solvents without further purification and produced the corresponding π-conjugated polymer with a molecular weight and yield comparable to those obtained under conventional oxygen-and moisture-free conditions. The facile synthetic protocol was applicable to the synthesis of other thienopyrroledione-based π-conjugated polymers. The obtained polymers served as semiconducting materials in organic light-emitting diodes (OLEDs) and organic photovoltaics. The effects of the terminal structure of the polymer on its photoluminescence and OLED device characteristics were also evaluated.

Synthesis of conjugated polymers via cyclopentannulation reaction: promising materials for iodine adsorption

“…The design of new conjugated polymers has become one of the chief topics of interest for scientific endeavors because of the importance of this latter class of materials in diverse applications, namely, light-emitting diodes (LEDs), [1][2][3] organic solar cells, [4][5][6][7] field-effect transistors (FETs), [8][9][10][11][12][13][14][15][16] sensors, 17 optical switches, [18][19][20][21][22] batteries, 23 and thermoelectrics. 24 In addition to the hitherto mentioned applications, conjugated microporous polymers (CMP) have become exceptionally eminent due to many reasons, notably their extended π-conjugation skeleton, high stability, synthesis versatility, large surface area, and excellent gas sorption properties.…”

Poly(1,4-phenylene vinylene) Derivatives with Ether Substituents to Improve Polymer Solubility for Use in Organic Light-Emitting Diode Devices

“…53 While the characteristics of the polymer are critical to device performance, the effectiveness of the device is also dependent on designing an architecture that has a good band gap overlap between layers. 6…”

“…1−5 Since then, many modifications have been made to improve polymer processability, device efficiency, emission wavelength, and turn-on voltage. 6−10 However, unsubstituted PPV is known to be insoluble and infusible, and because the oft-cited advantage of polymeric materials over small molecules in electronic devices is ease of processability, the search for soluble conjugated polymers has been extensive. Methods to improve solubility include the introduction of solubilizing side groups on the PPV structure, introduction of soluble polymers to yield PPV copolymers, and introduction of flexible blocks.…”

Highly Regioselective Direct C-H Arylation: Facile Construction of Symmetrical Dithienophthalimide-Based π -Conjugated Molecules for Optoelectronics

“…Direct C-H arylation offers an effective methodology for the functionalization of electron-deficient moieties without electrophilic substitution or strongly nucleophilic intermediates. To date, only quite a limited number of electron-deficient moieties have been reported to be suitable for direct C-H arylation such as benzothiadiazoles (BT) [44], thienopyrazines (TPz) [45], and thienopyrrolediones (TPD) (Scheme 1) [46]. In order to construct diverse organic π-conjugated molecules as efficient active materials for various potential applications, the screening and development of novel building blocks especially those with electron-deficient moieties suitable for direct C-H arylation are preferred but challenging.…”

“…For these reasons mentioned above, the selectivity and regioselectivity issues have been considered the Achilles heel of C-H arylation. Although a variety of direct C-H arylation has been explored [34][35][36][37][38][39][44][45][46], the selective direct C-H arylation reactions are still relatively rare [50,[57][58][59]. Controllable direct C-H arylation with high selectivity and regioselectivity is thus highly desirable yet remains a formidable challenge.…”