N → B Ladder Polymers Prepared by Postfunctionalization: Tuning of Electron Affinity and Evaluation as Acceptors in All-Polymer Solar Cells

Markus Grandl; Jonas Schepper; Sudeshna Maity; Andreas Peukert; Elizabeth Von Hauff; Frank Pammer

doi:10.1021/acs.macromol.8b02595

N → B Ladder Polymers Prepared by Postfunctionalization: Tuning of Electron Affinity and Evaluation as Acceptors in All-Polymer Solar Cells

Markus Grandl, Jonas Schepper, Sudeshna Maity, Andreas Peukert, Elizabeth Von Hauff^*, Frank Pammer

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

279 Downloads (Pure)

Abstract

A poly(biphenylene-pyrazinylene) (PPz, E _g ^opt = 3.10 eV) and a head-to-tail regioregular polypyridine (rr-P4Py, E _g ^opt = 3.25 eV) equipped with 1-alkenyl side chains have been prepared and postfunctionalized by hydroboration with different hydroboranes (9H-BBN, (C ₆ F ₅ ) ₂ B-H (BPF-H), Cl ₂ B-H) to give the corresponding ladder polymers featuring intramolecular coordinative N → B bonds. Characterization of the optical and electrochemical properties of the postfunctionalized polymers shows that the borylation strongly increases their electron affinity and lowers the optical gaps. Electron affinities between -3.75 eV (PPzBBN, E _g ^opt = 2.16 eV) and -4.35 eV (PPzBPF, E _g ^opt = 2.07 eV) can be reached for hydroborated PPz, while rr-P4Py-derivatives reach LUMO levels of -3.45 eV (P4PyBBN, E _g ^opt = 2.88 eV), -3.85 eV (P4PyBPF, E _g ^opt = 2.95 eV), and -4.15 eV (P4PyBCl ₂ , E _g ^opt = 2.95 eV). The potential of this class of compounds as electron acceptors is demonstrated by the investigation of the semiconducting properties of PPzBBN and PPzBPF, which showed ambipolar charge transport with hole and electron mobilities in order of 2 × 10 ^-5 cm ² V ^-1 s ^-1 . The polymers were tested as acceptors in all-polymer solar cells, which yielded functioning devices, with open-circuit voltages that directly reflect the electron affinity of the employed acceptor.

Original language	English
Pages (from-to)	1013-1024
Number of pages	12
Journal	Macromolecules
Volume	52
Issue number	3
Early online date	24 Jan 2019
DOIs	https://doi.org/10.1021/acs.macromol.8b02595
Publication status	Published - 12 Feb 2019

Funding

*(E.v.H.) E-mail: [email protected]. *(F.P.) E-mail: [email protected]. ORCID Elizabeth von Hauff: 0000-0002-6269-0540 Frank Pammer: 0000-0002-3869-0196 Author Contributions M.G., J.S., and S.M. contributed equally. Funding The authors thank the German Chemical Industry Fund (FCI, Liebig Scholarship to F.P. and doctoral scholarship to M.G.) the German Science Foundation (DFG), and The Netherlands Organization for Scientific Research (NWO) for funding for financial support (V0714M-13MV60 to E.v.H.). Notes The authors declare no competing financial interest.

Funders	Funder number
German Chemical Industry Fund
German Science Foundation
Netherlands Organization for Scientific Research
Five Colleges
Deutsche Forschungsgemeinschaft
Nederlandse Organisatie voor Wetenschappelijk Onderzoek	V0714M-13MV60

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acs.macromol.8b02595

acs.macromol.8b02595_N to B Ladder Polymers Prepared by PostfunctionalizationFinal published version, 4.51 MBLicence: Article 25fa Dutch Copyright Act

Persistent URL (handle)

Persistent link

Cite this

@article{49c5c6ae93bd4a10a2cc68622c2ed850,

title = "N → B Ladder Polymers Prepared by Postfunctionalization: Tuning of Electron Affinity and Evaluation as Acceptors in All-Polymer Solar Cells",

abstract = " A poly(biphenylene-pyrazinylene) (PPz, E g opt = 3.10 eV) and a head-to-tail regioregular polypyridine (rr-P4Py, E g opt = 3.25 eV) equipped with 1-alkenyl side chains have been prepared and postfunctionalized by hydroboration with different hydroboranes (9H-BBN, (C 6 F 5 ) 2 B-H (BPF-H), Cl 2 B-H) to give the corresponding ladder polymers featuring intramolecular coordinative N → B bonds. Characterization of the optical and electrochemical properties of the postfunctionalized polymers shows that the borylation strongly increases their electron affinity and lowers the optical gaps. Electron affinities between -3.75 eV (PPzBBN, E g opt = 2.16 eV) and -4.35 eV (PPzBPF, E g opt = 2.07 eV) can be reached for hydroborated PPz, while rr-P4Py-derivatives reach LUMO levels of -3.45 eV (P4PyBBN, E g opt = 2.88 eV), -3.85 eV (P4PyBPF, E g opt = 2.95 eV), and -4.15 eV (P4PyBCl 2 , E g opt = 2.95 eV). The potential of this class of compounds as electron acceptors is demonstrated by the investigation of the semiconducting properties of PPzBBN and PPzBPF, which showed ambipolar charge transport with hole and electron mobilities in order of 2 × 10 -5 cm 2 V -1 s -1 . The polymers were tested as acceptors in all-polymer solar cells, which yielded functioning devices, with open-circuit voltages that directly reflect the electron affinity of the employed acceptor. ",

author = "Markus Grandl and Jonas Schepper and Sudeshna Maity and Andreas Peukert and {Von Hauff}, Elizabeth and Frank Pammer",

year = "2019",

month = feb,

day = "12",

doi = "10.1021/acs.macromol.8b02595",

language = "English",

volume = "52",

pages = "1013--1024",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "3",

}

TY - JOUR

T1 - N → B Ladder Polymers Prepared by Postfunctionalization

T2 - Tuning of Electron Affinity and Evaluation as Acceptors in All-Polymer Solar Cells

AU - Grandl, Markus

AU - Schepper, Jonas

AU - Maity, Sudeshna

AU - Peukert, Andreas

AU - Von Hauff, Elizabeth

AU - Pammer, Frank

PY - 2019/2/12

Y1 - 2019/2/12

N2 - A poly(biphenylene-pyrazinylene) (PPz, E g opt = 3.10 eV) and a head-to-tail regioregular polypyridine (rr-P4Py, E g opt = 3.25 eV) equipped with 1-alkenyl side chains have been prepared and postfunctionalized by hydroboration with different hydroboranes (9H-BBN, (C 6 F 5 ) 2 B-H (BPF-H), Cl 2 B-H) to give the corresponding ladder polymers featuring intramolecular coordinative N → B bonds. Characterization of the optical and electrochemical properties of the postfunctionalized polymers shows that the borylation strongly increases their electron affinity and lowers the optical gaps. Electron affinities between -3.75 eV (PPzBBN, E g opt = 2.16 eV) and -4.35 eV (PPzBPF, E g opt = 2.07 eV) can be reached for hydroborated PPz, while rr-P4Py-derivatives reach LUMO levels of -3.45 eV (P4PyBBN, E g opt = 2.88 eV), -3.85 eV (P4PyBPF, E g opt = 2.95 eV), and -4.15 eV (P4PyBCl 2 , E g opt = 2.95 eV). The potential of this class of compounds as electron acceptors is demonstrated by the investigation of the semiconducting properties of PPzBBN and PPzBPF, which showed ambipolar charge transport with hole and electron mobilities in order of 2 × 10 -5 cm 2 V -1 s -1 . The polymers were tested as acceptors in all-polymer solar cells, which yielded functioning devices, with open-circuit voltages that directly reflect the electron affinity of the employed acceptor.

AB - A poly(biphenylene-pyrazinylene) (PPz, E g opt = 3.10 eV) and a head-to-tail regioregular polypyridine (rr-P4Py, E g opt = 3.25 eV) equipped with 1-alkenyl side chains have been prepared and postfunctionalized by hydroboration with different hydroboranes (9H-BBN, (C 6 F 5 ) 2 B-H (BPF-H), Cl 2 B-H) to give the corresponding ladder polymers featuring intramolecular coordinative N → B bonds. Characterization of the optical and electrochemical properties of the postfunctionalized polymers shows that the borylation strongly increases their electron affinity and lowers the optical gaps. Electron affinities between -3.75 eV (PPzBBN, E g opt = 2.16 eV) and -4.35 eV (PPzBPF, E g opt = 2.07 eV) can be reached for hydroborated PPz, while rr-P4Py-derivatives reach LUMO levels of -3.45 eV (P4PyBBN, E g opt = 2.88 eV), -3.85 eV (P4PyBPF, E g opt = 2.95 eV), and -4.15 eV (P4PyBCl 2 , E g opt = 2.95 eV). The potential of this class of compounds as electron acceptors is demonstrated by the investigation of the semiconducting properties of PPzBBN and PPzBPF, which showed ambipolar charge transport with hole and electron mobilities in order of 2 × 10 -5 cm 2 V -1 s -1 . The polymers were tested as acceptors in all-polymer solar cells, which yielded functioning devices, with open-circuit voltages that directly reflect the electron affinity of the employed acceptor.

UR - http://www.scopus.com/inward/record.url?scp=85060677075&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85060677075&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.8b02595

DO - 10.1021/acs.macromol.8b02595

M3 - Article

AN - SCOPUS:85060677075

SN - 0024-9297

VL - 52

SP - 1013

EP - 1024

JO - Macromolecules

JF - Macromolecules

IS - 3

ER -

N → B Ladder Polymers Prepared by Postfunctionalization: Tuning of Electron Affinity and Evaluation as Acceptors in All-Polymer Solar Cells

Abstract

Funding

UN SDGs

Access to Document

Persistent URL (handle)

Other files and links

Fingerprint

Cite this