Hydrogen Bonds Control Single-Chain Conformation, Crystallinity, and Electron Transport in Isoelectronic Diketopyrrolopyrrole Copolymers
- Qian WangQian WangTechnische Universität Chemnitz, Institut für Chemie, Straße der Nationen 62, Chemnitz 09111, GermanyMore by Qian Wang,
- Steffen BöckmannSteffen BöckmannInstitut für Physikalische Chemie, Westfälische Wilhelms-Universität, Corrensstraße 28, Münster 48149, GermanyMore by Steffen Böckmann,
- Florian GüntherFlorian GüntherUniversidade de São Paulo, Instituto de Física de São Carlos, CP 369, 13660-970, São Carlos, São Paulo 05508-900, BrazilMore by Florian Günther,
- Martin StreiterMartin StreiterTechnische Universität Chemnitz, Institut für Physik, Reichenhainer Str. 70, Chemnitz 09126, GermanyMore by Martin Streiter,
- Mario ZersonMario ZersonTechnische Universität Chemnitz, Institut für Physik, Reichenhainer Str. 70, Chemnitz 09126, GermanyMore by Mario Zerson,
- Alberto D. ScaccabarozziAlberto D. ScaccabarozziCenter for Nano Science and [email protected], Istituto Italiano di Tecnologia, Via Pascoli 70/3, Milano 20133, ItalyMore by Alberto D. Scaccabarozzi,
- Wen Liang TanWen Liang TanDepartment of Materials Science and Engineering, Monash University, Clayton 3800, Victoria, AustraliaMore by Wen Liang Tan,
- Hartmut KomberHartmut KomberLeibniz Institut für Polymerforschung Dresden e. V., Hohe Straße 6, Dresden 01069, GermanyMore by Hartmut Komber,
- Carsten DeibelCarsten DeibelTechnische Universität Chemnitz, Institut für Physik, Reichenhainer Str. 70, Chemnitz 09126, GermanyMore by Carsten Deibel,
- Robert MagerleRobert MagerleTechnische Universität Chemnitz, Institut für Physik, Reichenhainer Str. 70, Chemnitz 09126, GermanyMore by Robert Magerle,
- Sibylle GemmingSibylle GemmingTechnische Universität Chemnitz, Institut für Physik, Reichenhainer Str. 70, Chemnitz 09126, GermanyCenter for Materials, Architectures and Integration of Nanomembranes (MAIN), Technische Universität Chemnitz, Rosenbergstr. 6, Chemnitz 09126, GermanyMore by Sibylle Gemming,
- Christopher R. McNeillChristopher R. McNeillDepartment of Materials Science and Engineering, Monash University, Clayton 3800, Victoria, AustraliaMore by Christopher R. McNeill,
- Mario CaironiMario CaironiCenter for Nano Science and [email protected], Istituto Italiano di Tecnologia, Via Pascoli 70/3, Milano 20133, ItalyMore by Mario Caironi,
- Michael Ryan HansenMichael Ryan HansenInstitut für Physikalische Chemie, Westfälische Wilhelms-Universität, Corrensstraße 28, Münster 48149, GermanyMore by Michael Ryan Hansen, and
- Michael Sommer*Michael Sommer*Email: [email protected]Technische Universität Chemnitz, Institut für Chemie, Straße der Nationen 62, Chemnitz 09111, GermanyCenter for Materials, Architectures and Integration of Nanomembranes (MAIN), Technische Universität Chemnitz, Rosenbergstr. 6, Chemnitz 09126, GermanyMore by Michael Sommer
Abstract
The combination of computational methods and advanced characterization techniques is used to highlight the role of the intramolecular hydrogen bond in thienyldiketopyrrolopyrrole (ThDPPTh) copolymerized with tetrafluorobenzene (F4) to PThDPPThF4. We investigate how the torsion potentials of ThDPPTh and isoelectronic dithiazolyldiketopyrrolopyrrole (TzDPPTz) are influenced by hydrogen bonding and translate into different conformation, molecular, structural, and opto-electronic characteristics. ThDPPTh exhibits N,S-syn orientation in the most stable conformer locked by an intramolecular hydrogen bond. In TzDPPTz, such a hydrogen bond is not possible, which leads to a “ring flip” and makes the N,S-anti conformer most stable. Copolymers with F4, PThDPPThF4 and PTzDPPTzF4, exhibit straight and curved backbones, respectively, but similar chain rigidity. These conformations are experimentally confirmed by local packing motifs from solid-state NMR spectroscopy. The differences in conformation strongly influence the opto-electronic and structural properties. X-ray scattering and atomic force microscopy reveal lamellar morphologies of both PThDPPThF4 and PTzDPPTzF4, but increased long range order, reduced paracrystallinity, and larger domains of the former. In-depth analysis of solid-state NMR spectra allows for obtaining information on absolute degrees of crystallinity, which are substantially higher for PThDPPThF4. These differences in structural properties cause field-effect electron mobilities of PThDPPThF4 to be larger by a factor of 20.
Cited By
This article has not yet been cited by other publications.