Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Abstract

Three vinylene linked diketopyrrolopyrrole based donor-acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V(-1) s(-1).

Synthesis of Pyrrole‐Based Poly(arylenevinylene)s via Co‐Catalyzed Hydroarylation of Alkynes

“…[ 1–4 ] Poly(arylenevinylene)s (PAVs) are an attractive family of π ‐conjugated polymers, for which a large number of applications have been reported. [ 5–9 ] PAVs have generally been prepared by polycondensation [ 10 ] based on the Gilch reaction, [ 11,12 ] Wittig reaction, [ 13–15 ] Knoevenagel reaction, [ 16,17 ] olefin metathesis, [ 18–24 ] Suzuki‐Miyaura cross‐coupling, [ 25 ] Migita‐Kosugi‐Stille cross‐coupling, [ 26 ] and Mizoroki‐Heck reaction. [ 27–29 ] However, these polycondensation reactions also produce stoichiometric amounts of by‐products derived from the reactive functional groups of the monomers ( Scheme a), thereby necessitating tedious purification steps.…”

Electrochemical Stability and Ambipolar Charge Transport in Diketopyrrolopyrrole-Based Organic Materials

“…19 In our group, we rationally designed and synthesized DPP-DPP-based copolymers and oligomers which exhibit bandlike and ambipolar charge transport properties. 20,21 In addition, ambipolar charge transport was realized by electrode design in rubrene-based organic semiconductors resulting in hole and electron mobilities of ∼22 and ∼5.0 cm 2 V −1 s −1 , respectively. 22,23 However, these studies have been carried out on π-conjugated oligomers and polymers possessing linear and one-dimensional chains.…”

Experimental and Theoretical Investigations of Different Diketopyrrolopyrrole-Based Polymers

“…10 As per the recent literature reports, fullerenes have emerged as the material of choice for acceptor moiety; diketopyrrolopyrrole (DPP)-based polymers 11 have been established as the most promising candidate for donor material in BHJSCs. 12−15 Particularly, DPP core 16,17 has attracted a lot of attention recently because it is a fused aromatic core with a strong electron withdrawing part. It consists of two carbonyl groups to enhance intramolecular or intermolecular interactions via π–π stacking of the polymer chains in solid states.…”