Charge‐Compensated N‐Doped π ‐Conjugated Polymers: Toward both Thermodynamic Stability of N‐Doped States in Water and High Electron Conductivity

The understanding and applications of electron-conducting π-conjugated polymers with naphtalene diimide (NDI) blocks show remarkable progress in recent years. Such polymers demonstrate a facilitated n-doping due to the strong electron deficiency of the main polymer chain and the presence of the positively charged side groups stabilizing a negative charge of the n-doped backbone. Here, the n-type conducting NDI polymer with enhanced stability of its n-doped states for prospective “in-water” applications is developed. A combined experimental–theoretical approach is used to identify critical features and parameters that control the doping and electron transport process. The facilitated polymer reduction ability and the thermodynamic stability in water are confirmed by electrochemical measurements and doping studies. This material also demonstrates a high conductivity of 10−2 S cm−1 under ambient conditions and 10−1 S cm−1 in vacuum. The modeling explains the stabilizing effects for various dopants. The simulations show a significant doping-induced “collapse” of the positively charged side chains on the core bearing a partial negative charge. This explains a decrease in the lamellar spacing observed in experiments. This study fundamentally enables a novel pathway for achieving both thermodynamic stability of the n-doped states in water and the high electron conductivity of polymers

Copolymerization of zinc-activated isoindigo- and naphthalene-diimide based monomers: an efficient route to low bandgap pi-conjugated random copolymers with tunable properties

The present work aims at the extension of the scope of a recently discovered polycondensation of AB-type anion-radical monomers. To this end, we investigate the polymerization of isoindigo-based monomer and its copolymerization with the naphthalenediimide-based monomer. Although polycondensations of parent naphthalenediimide- and perylenediimide-based monomers involve chain-growth mechanism, we found that the corresponding isoindigo-based monomer polymerizes in a step-growth manner under the same reaction conditions. In contrast to Stille, Suzuki and direct arylation polycondensations which require prolonged stirring at high temperatures, the polymerization approach we employed in this study proceeds fast at room temperature. It was found that near statistical copolymerization of isoindigo-based anion-radical monomers with corresponding naphtalenediimide-based monomers proceeds smoothly resulting in a library of copolymers with varying composition and properties depending on the ratio of the monomers

Rotational Dynamics of Spin-Labeled Polyacid Chain Segments in Polyelectrolyte Complexes Studied by CW EPR Spectroscopy

A nitroxide spin label has been covalently linked to the weak polyacid poly­(ethylene-<i>alt</i>-maleic acid) (P­(E-<i>alt</i>-MA)) to study the rotational mobility of the polyacid backbone in polyelectrolyte complexes (PEC) formed with the oppositely charged strong polycation poly­(diallyldi­methylammonium chloride) (PDADMAC) in dependence on the pH of the dispersion and the temperature. The rotational mobility of the polyacid chain segments has been determined by simulation of the line shape of the continuous wave (CW) electron paramagnetic resonance (EPR) spectra using the microscopic order/macroscopic disorder (MOMD) model of restricted rotational diffusion. The study has shown that the diffusion coefficient characterizing the rotational motions of the polyacid backbone is significantly smaller at low degree of dissociation at pH 4 than at high degree of dissociation at pH 7 and pH 10

Copolymerization of zinc-activated isoindigo- and naphthalene-diimide based monomers: an efficient route to low bandgap π-conjugated random copolymers with tunable properties

The present work aims at the extension of the scope of a recently discovered polycondensation of AB-type anion-radical monomers. To this end, we investigate the polymerization of isoindigo-based monomer and its copolymerization with the naphthalenediimide-based monomer. Although polycondensations of parent naphthalenediimide- and perylenediimide-based monomers involve chain-growth mechanism, we found that the corresponding isoindigo-based monomer polymerizes in a step-growth manner under the same reaction conditions. In contrast to Stille, Suzuki and direct arylation polycondensations which require prolonged stirring at high temperatures, the polymerization approach we employed in this study proceeds fast at room temperature. It was found that near statistical copolymerization of isoindigo-based anion-radical monomers with corresponding naphtalenediimide-based monomers proceeds smoothly resulting in a library of copolymers with varying composition and properties depending on the ratio of the monomers

A Chemically Doped Naphthalenediimide-Bithiazole Polymer for n-Type Organic Thermoelectrics

The synthesis of a novel naphthalenediimide (NDI)-bithiazole (Tz2)-based polymer [P(NDI2OD-Tz2)] is reported, and structural, thin-film morphological, as well as charge transport and thermoelectric properties are compared to the parent and widely investigated NDI-bithiophene (T2) polymer [P(NDI2OD-T2)]. Since the steric repulsions in Tz2 are far lower than in T2, P(NDI2OD-Tz2) exhibits a more planar and rigid backbone, enhancing p-p chain stacking and intermolecular interactions. In addition, the electron-deficient nature of Tz2 enhances the polymer electron affinity, thus reducing the polymer donor-acceptor character. When n-doped with amines, P(NDI2OD-Tz2) achieves electrical conductivity (approximate to 0.1 S cm(-1)) and a power factor (1.5 mu W m(-1) K-2) far greater than those of P(NDI2OD-T2) (0.003 S cm(-1) and 0.012 mu W m(-1) K-2, respectively). These results demonstrate that planarized NDI-based polymers with reduced donor-acceptor character can achieve substantial electrical conductivity and thermoelectric response.Funding Agencies|Knut and Alice Wallenberg Foundation; Swedish Foundation for Strategic Research; VINNOVA [2015-04859]; Swedish Research Council [2016-03979]; Advanced Functional Materials Center at Linkoping University [2009-00971]; U.S. Department of Commerce, National Institute of Standards and Technology, Center for Hierarchical Materials Design (CHiMaD) [70NANB14H012]; DOE Office of Science [DE-AC02-06CH11357]; DFG within the CoEcfaed [KI-1094/9, FA 1502/1-1]; Humboldt Foundation</p

Molecular Doping of a High Mobility Diketopyrrolopyrrole–Dithienylthieno[3,2‑<i>b</i>]thiophene Donor–Acceptor Copolymer with F6TCNNQ

Herein we present a molecular doping of a high mobility diketopyrrolopyrrole–dithienylthieno­[3,2-<i>b</i>]­thiophene donor–acceptor copolymer poly­[3,6-(dithiophene-2-yl)-2,5-di­(6-dodecyl­octadecyl)­pyrrolo­[3,4-<i>c</i>]­pyrrole-1,4-dione-<i>alt</i>-thieno­[3,2-<i>b</i>]­thiophene], PDPP­(6-DO)₂TT, with the electron-deficient compound hexafluoro­tetracyano­naphthoquino­dimethane (F6TCNNQ). Despite a slightly negative HOMO_donor–LUMO_acceptor offset of −0.12 eV which may suggest a reduced driving force for the charge transfer (CT), a partial charge CT was experimentally observed in PDPP­(6-DO)₂TT:F6TCNNQ by absorption, vibrational, and electron paramagnetic resonance spectroscopies and predicted by density functional theory calculations. Despite the modest CT, PDPP­(6-DO)₂TT:F6TCNNQ films possess unexpectedly high conductivities up to 2 S/cm (comparable with the conductivities of the benchmark doped polymer system P3HT:F4TCNQ having a large positive offset). The observation of the high conductivity in doped PDPP­(6-DO)₂TT films can be explained by a high hole mobility in PDPP­(6-DO)₂TT blends which compensates a lowered (relatively to P3HT:F4TCNQ) concentration of free charge carriers. We also show that F6TCNNQ-doped P3HT, the system which has not been reported so far to the best of our knowledge, exhibits a conductivity up to 7 S/cm, which exceeds the conductivity of the benchmark P3HT:F4TCNQ system