Thieno-, Furo-, and Selenopheno[3,4-c]pyrrole-4,6-dione Copolymers: Effect of the Heteroatom on the Electrooptical Properties

Abstract

New push−pull conjugated polymers based on furo [3,4-c]pyrrole-4,6-dione (FPD) and selenopheno [3,4-c]pyrrole-4,6-dione (SePD) have been synthesized and compared with their thieno [3,4-c]pyrrole-4,6-dione (TPD) analogues to investigate the effects of the heteroatom on the electrooptical properties. The copolymers were synthesized using either Stille cross-coupling or direct heteroarylation polymerization (DHAP), the latter method giving high molecular weights. Hypsochromic shifts of the band gaps were observed for FPDbased copolymers (sulfur substituted by oxygen) while small bathochromic shift was observed for SePD (sulfur substituted by selenium) when compared to its TPD analogue. These two new classes of conjugated polymers exhibit electrooptical properties that could lead to interesting bulk heterojunction plastic solar cells.

Computational study on the effects of substituent and heteroatom on physical properties and solar cell performance in donor-acceptor conjugated polymers based on benzodithiophene

“…In order to find an appropriate functional and basis set for the calculations of studied polymers, we choose three hybrid functionals including PBE0 [19], PBEh1PBE [20], and mPW1PBE [19] at 6-31G* and 6-311G* basis sets to calculate the dimer models of PBSA and PBSeA. As shown in Table S1 and Table S2, the calculated results of HOMO energy levels at mPW1PBE/6-31G* level (−5.50 and −5.48 eV for DBSA and DBSeA, respectively; here "D" means dimer) agree well with the experimental values of the polymers (−5.56 and −5.51 eV for PBSA and PBSeA, respectively) [21]. Thus, the ground state geometries of all dimers and monomers were optimized in gas-phase within the mPW1PBE functional, using 6-31G* basis set, meanwhile the HOMO energy levels of dimers were predicted.…”

“…As listed in Table S3-S6, all vertical electronic transition energy of the first excited states (S1) and oscillator strength (f) are smaller in gas phase than in chloroform solution, but the energy gaps and f of the second exited states (S2) are almost unchanged. Among those methods, the TD-O3LYP/6-311G* approach in chloroform solution (2.08 and 2.04 eV for DBSA and DBSeA, respectively) is the best choice to save computational time and in agreement with the experimental values (2.03 and 1.95 eV for PBSA and PBSeA, respectively) [21]. Moving to the direct comparison of normalized experimental absorption spectra and calculated spectra at O3LYP/6-311G* level in chloroform solution for PBSA and PBSeA, reported in Fig.…”

Triazolobenzothiadiazole‐Based Copolymers for Polymer Light‐Emitting Diodes: Pure Near‐Infrared Emission via Optimized Energy and Charge Transfer

“…[15] Tail-to-tail alkylation of the 2T moiety in an analogous polymer lowers the LUMO to −3.97 eV, which is in the same level with that of P2TTPD-0. [16] We expect the steric hindrance among the head-to-head side chains to induce torsion to the 2T R sites of the P2TTPD-0 backbone, which lowers the HOMO level, reduces the π-π stacking and promotes amorphous property in the solid state. [17] P2TTPD-0.5, P2TTPD-1.0, P2TTPD-2.5, and P2TTPD-10 have almost identical HOMO/ LUMO levels with P2TTPD-0 and no E ox /E red were found for the TBTTT segment using the CV method.…”

Organometallic Approaches to Conjugated Polymers for Plastic Solar Cells: From Laboratory Synthesis to Industrial Production

“…[57b,71] Table 5 , [168] and the values are referred to elemental species; the actual amounts of wastes are larger and depend on the chemical nature of the byproducts. The large amount of tin to be disposed of if Stille polymerization is carried out is immediately evident (tin wastes are even greater in quantity, in view of the fact that a superstoichiometric amount of trialkyltin chloride derivatives is used for the monomer preparation).…”