Polymerization of Tellurophene Derivatives by Microwave‐Assisted Palladium‐Catalyzed ipso‐Arylative Polymerization

Abstract

We report the synthesis of a tellurophene-containing low-bandgap polymer, PDPPTe2T, by microwave-assisted palladium-catalyzed ipso-arylative polymerization of 2,5bis[(a-hydroxy-a,a-diphenyl)methyl]tellurophene with a diketopyrrolopyrrole (DPP) monomer. Compared with the corresponding thiophene analog, PDPPTe2T absorbs light of longer wavelengths and has a smaller bandgap. Bulk heterojunction solar cells prepared from PDPPTe2T and PC 71 BM show PCE values of up to 4.4 %. External quantum efficiency measurements show that PDPPTe2T produces photocurrent at wavelengths up to 1 mm. DFT calculations suggest that the atomic substitution from sulfur to tellurium increases electronic coupling to decrease the length of the carbon-carbon bonds between the tellurophene and thiophene rings, which results in the red-shift in absorption upon substitution of tellurium for sulfur.Supporting information for this article (general experimental details, synthesis and characterization for compounds, UV/Vis absorption spectra, cyclic voltammetry, gel-permeation chromatography, details of device fabrications, computation details, and NMR spectra) is available on the WWW under http://dx.

Tellurophene-Based Random Copolymers for High Responsivity and Detectivity Photodetectors

“…34,35 For example, Grubbs reported organic photovoltaic devices based on tellurophene-containing polymers and achieved a comparable power conversion efficiency (PCE) of 4.4% with its thiophene analogues but a much higher photocurrent. 30 McCulloch et al constructed a series of thieno [3,2-b]thiophene diketopyrrolopyrrole-based copolymers with chalcogenphene comonomers units (thiophene, selenophene, and tellurophene). Upon tuning the chalcogenphene moieties, the photovoltaic performances were systematically tuned.…”

Redox chemistry of π-extended tellurophenes

“…Most of these reactions involve transition metal complexes, however, recent emphasis has been placed on main group inorganic compounds due to their lightweight and more abundant nature [1][2][3][4][5][6] . In this context, tellurophene, a telluriumcontaining five-membered aromatic ring 7,8 , is of particular interest given that its π-delocalized nature resembles more traditional aromatic heterocycles and that it incorporates a metalloid that is capable of several stable oxidation states 9-11 . In the last decade, the incorporation of the tellurophene-motif into π-extended molecules and polymers has been recognized as a promising design for electronic devices, such as thin film transistors, light emitters, photovoltaics, and thermoelectrics [12][13][14][15][16][17][18][19][20][21][22][23][24][25] . In comparison with thiophene-containing or selenophenecontaining counterparts, characteristic properties derived from Te atom have been reported.…”

An Updated Strategy for Designing Non-Fullerene Acceptors by the Lowest Singlet and Triplet States Excitation: Influence of Periodical Substitution from O, S, and Se to Te for BAE Derivatives

“…Note that X atom was located in a six-membered ring. If atomic replacement does not occur in the five-membered ring, then the corresponding rule (tellurophene and selenophene replacement thiophene can reduce E g 22,23 and so on) would not be a general one. To characterize the ability of accepting electrons for BAEs, 45,46 LUMO energy levels for all molecules were listed in Figure 3.…”

“…Te atoms were represented by the LANL2DZ effective core potential and its corresponding basis set in the paper. 22,41 All calculations mentioned above were performed in the Gaussian 09 software package. 42 O, from T to syn-folded, and the energy barrier is rapidly increased by more than two times, near or greater than 100 kJ/mol (it is necessary to convert conformation through some specific conditions).…”

“…21 In the same year, they synthesized a tellurophene-containing polymer PDPPTe2T, compared with the corresponding thiophene analog, which has longer wavelengths and a smaller bandgap due to increased electronic coupling; the PCE of PDPPTe2T:PC 71 BM based BHJ devices reached 4.40%. 22 A series of diketopyrrolopyrrole-based copolymers with different chalcogenophene comonomers (thiophene, selenophene, and tellurophene) were synthesized by Ashraf and co-workers; the results indicated that the bandgap was reduced and intermolecular heteroatom− heteroatom interactions were increased as group 16 enlarged, affording an excellent efficiency of 7.10−8.80% matching with fullerene derivative acceptors. 23 This strategy using heavy atoms is also applied to NF acceptors to improve photovoltaic performance of materials.…”