Molecular Dioxygen‐Mediated Passivation of Electron Traps in n‐Type Organic Charge‐Transfer Complexes

K Kirill K. Gubanov (Physical Chemistry II Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) Y Yana Reva (Physical Chemistry I Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) C Christian L. Ritterhoff (Computer Chemistry Center (CCC) Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) F Fabio Candolfi (Applied Physics Department of Physics Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) D Daniel Langford (Physical Chemistry I Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) M Maximilian Herm (Physical Chemistry I Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) E Evanie Franz (Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany) R Ryan W. Crisp (Chemistry of Thin Film Materials Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) F Frank Hampel (Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuremberg, Nikolaus-Fiebiger-Strasse 10, Erlangen 91058, Germany) M Michael Krieger (Applied Physics Department of Physics Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) A Andreas Späth (Physical Chemistry II Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) B Benjamin Watts (Paul Scherrer Institute Villigen Switzerland) J Jörg Libuda (Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany) H Heiko B. Weber (Interdisciplinary Center for Molecular Materials (ICMM) Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany) B Bernd Meyer (Computer Chemistry Center (CCC) & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052 Erlangen, Germany) D Dirk M. Guldi (Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstrasse 3, Erlangen 91058, Germany) R Rainer H. Fink (Physical Chemistry II Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany)

Abstract

ABSTRACT The inherent susceptibility of n‐type organic semiconductors to molecular dioxygen (O 2 ) results in electron trapping or in unintended p‐doping, which in turn diminishes their electron mobility. This concept is challenged in the present study by exploring O 2 interactions with organic charge‐transfer complexes (CTCs), where electron donor–acceptor interactions generate partially delocalized electronic states. Using a CTC comprising a phenazine electron donor and a 7,7,8,8‐tetracyanoquinodimethane (TCNQ) electron acceptor, we demonstrate that its exposure to O 2 does not lead to electron extraction but instead enhances the charge‐transfer activity. The increased electron density at the TCNQ acceptor upon CTC exposure to O 2 is attributed to electron trap‐states passivation by O 2 , without evidence of chemisorption. This passivation mitigates recombination losses, resulting in a threefold photoluminescence quantum yield increase, enhanced electrical conductivity, and improved charge‐transfer state efficiency. Similar O 2 ‐mediated conductivity enhancements are observed across additional donor–acceptor pairs, proving the broader applicability of this effect, and paving the way for designing O 2 ‐enhanced advanced organic electronic materials.

Article Details

Volume / Issue Vol. 65, Issue 33
Published August 10, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (17)

K

Kirill K. Gubanov

Physical Chemistry II Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

Y

Yana Reva

Physical Chemistry I Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

C

Christian L. Ritterhoff

Computer Chemistry Center (CCC) Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

F

Fabio Candolfi

Applied Physics Department of Physics Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

D

Daniel Langford

Physical Chemistry I Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

M

Maximilian Herm

Physical Chemistry I Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

E

Evanie Franz

Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany

R

Ryan W. Crisp

Chemistry of Thin Film Materials Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

F

Frank Hampel

Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-University Erlangen-Nuremberg, Nikolaus-Fiebiger-Strasse 10, Erlangen 91058, Germany

M

Michael Krieger

Applied Physics Department of Physics Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

A

Andreas Späth

Physical Chemistry II Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

B

Benjamin Watts

Paul Scherrer Institute Villigen Switzerland

J

Jörg Libuda

Interface Research and Catalysis, ECRC, Friedrich-Alexander-Universität Erlangen-Nürnberg, 91058 Erlangen, Germany

H

Heiko B. Weber

Interdisciplinary Center for Molecular Materials (ICMM) Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany

B

Bernd Meyer

Computer Chemistry Center (CCC) & Interdisciplinary Center for Molecular Materials (ICMM), Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052 Erlangen, Germany

D

Dirk M. Guldi

Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials, Friedrich-Alexander University Erlangen-Nürnberg, Egerlandstrasse 3, Erlangen 91058, Germany

R

Rainer H. Fink

Physical Chemistry II Department of Chemistry and Pharmacy Friedrich‐Alexander‐Universität Erlangen‐Nürnberg Erlangen Germany