Spectroscopic Studies of Charge-Transfer Character and Photoresponses of F4TCNQ-Based Donor–Acceptor Complexes

Barrett, Brandon J.; Saund, Simran S.; Dziatko, Rachel A.; Clark-Winters, Tylar L.; Katz, Howard E.; Bragg, Arthur E.

doi:10.1021/acs.jpcc.0c01372

Title: Spectroscopic Studies of Charge-Transfer Character and Photoresponses of F₄TCNQ-Based Donor–Acceptor Complexes

Journal Article · Thu Apr 02 00:00:00 EDT 2020 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.0c01372· OSTI ID:1773882

Barrett, Brandon J. ^[1]; Saund, Simran S. ^[1]; Dziatko, Rachel A. ^[1]; Clark-Winters, Tylar L. ^[1];

^[1];

^[1]

Johns Hopkins Univ., Baltimore, MD (United States)

F₄TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) is used widely as a hole-doping agent in photoresponsive organic semiconducting materials, yet relatively little is known about the photoresponses of the F₄TCNQ·^- anion generated via doping. Furthermore, there is still relatively little systematic exploration of how the properties of the local material or chemical environment impacts the driving force for generating these charge-transfer complexes. Here we present spectroscopic and photophysical studies of F₄TCNQ in charge-transfer complexes (CTCs) with the electron donor N,N’-Diphenyl-N-N’-di-p-tolylbenzene-1,4-diamine (MPDA) both in dichloroethane solution and polystyrene matrices. Integer charge transfer (ICT) between donor and acceptor occurs readily in dichloroethane solvent to form F₄TCNQ·^-:MPDA⁺ CTCs, due to a ~150 mV difference in MPDA⁺/MPDA and F₄TCNQ/F₄TCNQ·^- reduction potentials. Ultrafast spectroscopic studies of the CTC as well as electrochemically generated F₄TCNQ·^- and MDPA⁺ reveal that the photoresponses of these CTCs are dominated by that of the dopant anion, including rapid deactivation (800 fs) after excitation to the anion D₁ excited state, followed by slower (~10 ps) vibrational cooling in the anion D₀ state. Excitation to the higher-lying D₂ state results in a rapid relaxation to the D₁ state, in contrast to direct D₂-D₀ relaxation previously observed for F₄TCNQ·^- in gas phase. CTCs embedded in polystyrene (PS) matrices are observed to lose their integer charge-transfer character upon evaporation of solvent, as evidenced by changes to electronic and vibrational absorption features associated with F₄TCNQ·^-. This change is attributed to the loss of solvent stabilization of the ion pair formed through the charge-transfer reaction. Ultrafast spectral measurements reveal that the photoresponses of the partial charge-transfer (PCT) species embedded in PS are still highly similar to those of the ICT species and unlike that of neutral F₄TCNQ, implying the electronic properties of the PCT state are likewise dominated by properties of the reduced acceptor molecule. We conclude that excitation of ICT or PCT states introduces optical losses for photoresponses of doped organic semiconductor materials due to the large anion absorption cross section and its rapid, dissipative deactivation dynamics.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-07ER46465

OSTI ID:: 1773882

Journal Information:: Journal of Physical Chemistry. C, Vol. 124, Issue 17; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Doped Organic Transistors Lüssem, Björn; Keum, Chang-Min; Kasemann, Daniel Chemical Reviews, Vol. 116, Issue 22 https://doi.org/10.1021/acs.chemrev.6b00329	journal	October 2016
Doped organic transistors operating in the inversion and depletion regime Lüssem, Björn; Tietze, Max L.; Kleemann, Hans Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3775	journal	November 2013
Highly Efficient Organic Devices Based on Electrically Doped Transport Layers Walzer, K.; Maennig, B.; Pfeiffer, M. Chemical Reviews, Vol. 107, Issue 4 https://doi.org/10.1021/cr050156n	journal	April 2007
Enhanced Hole Injection into Amorphous Hole-Transport Layers of Organic Light-Emitting Diodes Using Controlled p-Type Doping Zhou, X.; Blochwitz, J.; Pfeiffer, M. Advanced Functional Materials, Vol. 11, Issue 4 https://doi.org/10.1002/1616-3028(200108)11:4<310::AID-ADFM310>3.0.CO;2-D	journal	August 2001
Controlling Molecular Doping in Organic Semiconductors Jacobs, Ian E.; Moulé, Adam J. Advanced Materials, Vol. 29, Issue 42 https://doi.org/10.1002/adma.201703063	journal	September 2017
Double doping of conjugated polymers with monomer molecular dopants Kiefer, David; Kroon, Renee; Hofmann, Anna I. Nature Materials, Vol. 18, Issue 2 https://doi.org/10.1038/s41563-018-0263-6	journal	January 2019
Excited electronic states of the anion of 7,7,8,8-tetracyanoquinodimethane (TCNQ) Skurski, P.; Gutowski, M. Journal of Molecular Structure: THEOCHEM, Vol. 531, Issue 1-3 https://doi.org/10.1016/S0166-1280(00)00467-X	journal	October 2000
Lead-Halide Perovskites Meet Donor–Acceptor Charge-Transfer Complexes Marchal, Nadège; Van Gompel, Wouter; Gélvez-Rueda, María C. Chemistry of Materials, Vol. 31, Issue 17 https://doi.org/10.1021/acs.chemmater.9b01289	journal	December 2018
Solution-processed thin films of a charge transfer complex for ambipolar field-effect transistors Salzillo, Tommaso; Campos, Antonio; Mas-Torrent, Marta Journal of Materials Chemistry C, Vol. 7, Issue 33 https://doi.org/10.1039/C9TC03064F	journal	January 2019
Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices Talin, A. Alec; Centrone, Andrea; Ford, Alexandra C. Science, Vol. 343, Issue 6166, p. 66-69 https://doi.org/10.1126/science.1246738	journal	December 2013
Electron transfer in a new highly conducting donor-acceptor complex Ferraris, John.; Cowan, D. O.; Walatka, V. Journal of the American Chemical Society, Vol. 95, Issue 3 https://doi.org/10.1021/ja00784a066	journal	February 1973
Substituted Quinodimethans. II. Anion-radical Derivatives and Complexes of 7,7,8,8-Tetracyanoquinodimethan Melby, L. R.; Harder, R. J.; Hertler, W. R. Journal of the American Chemical Society, Vol. 84, Issue 17 https://doi.org/10.1021/ja00876a029	journal	September 1962
The difference between metallic and insulating salts of tetracyanoquinodimethone (TCNQ): how to design an organic metal Torrance, Jerry B. Accounts of Chemical Research, Vol. 12, Issue 3 https://doi.org/10.1021/ar50135a001	journal	March 1979
Charge-transfer crystallites as molecular electrical dopants Méndez, Henry; Heimel, Georg; Winkler, Stefanie Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9560	journal	October 2015
Band Engineering and Majority Carrier Switching in Isostructural Donor–Acceptor Complexes DPTTA‐F _X TCNQ Crystals ( X = 1, 2, 4) Liang, Yingying; Qin, Yunke; Chen, Jie Advanced Science, Vol. 7, Issue 3 https://doi.org/10.1002/advs.201902456	journal	November 2019
Efficient ambipolar transport properties in alternate stacking donor–acceptor complexes: from experiment to theory Qin, Yunke; Cheng, Changli; Geng, Hua Physical Chemistry Chemical Physics, Vol. 18, Issue 20 https://doi.org/10.1039/C6CP01509C	journal	January 2016
Tuning of the degree of charge transfer and the electronic properties in organic binary compounds by crystal engineering: a perspective Jiang, Hui; Hu, Peng; Ye, Jun Journal of Materials Chemistry C, Vol. 6, Issue 8 https://doi.org/10.1039/C7TC04982J	journal	January 2018
Polymorphism controls the degree of charge transfer in a molecularly doped semiconducting polymer Jacobs, Ian E.; Cendra, Camila; Harrelson, Thomas F. Materials Horizons, Vol. 5, Issue 4 https://doi.org/10.1039/C8MH00223A	journal	January 2018
Electronic and Optical Properties of Oligothiophene-F4TCNQ Charge-Transfer Complexes: The Role of the Donor Conjugation Length Valencia, Ana M.; Cocchi, Caterina The Journal of Physical Chemistry C, Vol. 123, Issue 14 https://doi.org/10.1021/acs.jpcc.9b01390	journal	March 2019
Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules Salzmann, Ingo; Heimel, Georg; Oehzelt, Martin Accounts of Chemical Research, Vol. 49, Issue 3 https://doi.org/10.1021/acs.accounts.5b00438	journal	February 2016
Elementary steps in electrical doping of organic semiconductors Tietze, Max L.; Benduhn, Johannes; Pahner, Paul Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03302-z	journal	March 2018
Overcoming Film Quality Issues for Conjugated Polymers Doped with F ₄ TCNQ by Solution Sequential Processing: Hall Effect, Structural, and Optical Measurements Scholes, D. Tyler; Hawks, Steven A.; Yee, Patrick Y. The Journal of Physical Chemistry Letters, Vol. 6, Issue 23 https://doi.org/10.1021/acs.jpclett.5b02332	journal	November 2015
Introducing Solubility Control for Improved Organic P-Type Dopants Li, Jun; Zhang, Guangwu; Holm, Daniella M. Chemistry of Materials, Vol. 27, Issue 16 https://doi.org/10.1021/acs.chemmater.5b02340	journal	August 2015
Electronic states and anti-ferromagnetic order in mixed-stack charge-transfer compound (BEDT-TTF)(F2TCNQ) Hasegawa, T.; Kagoshima, S.; Mochida, T. Solid State Communications, Vol. 103, Issue 8 https://doi.org/10.1016/S0038-1098(97)00226-3	journal	August 1997
Charge Transport Properties of Perylene–TCNQ Crystals: The Effect of Stoichiometry Vermeulen, D.; Zhu, L. Y.; Goetz, K. P. The Journal of Physical Chemistry C, Vol. 118, Issue 42 https://doi.org/10.1021/jp508520x	journal	October 2014
N-type field-effect transistors based on layered crystalline donor–acceptor semiconductors with dialkylated benzothienobenzothiophenes as electron donors Tsutsumi, Jun'ya; Matsuoka, Satoshi; Inoue, Satoru Journal of Materials Chemistry C, Vol. 3, Issue 9 https://doi.org/10.1039/C4TC02481H	journal	January 2015
Organic metals Bryce, Martin R.; Murphy, Lynne C. Nature, Vol. 309, Issue 5964 https://doi.org/10.1038/309119a0	journal	May 1984
Hydrogen-Bond Interaction in Organic Conductors: Redox Activation, Molecular Recognition, Structural Regulation, and Proton Transfer in Donor−Acceptor Charge-Transfer Complexes of TTF-Imidazole Murata, Tsuyoshi; Morita, Yasushi; Yakiyama, Yumi Journal of the American Chemical Society, Vol. 129, Issue 35 https://doi.org/10.1021/ja072607m	journal	September 2007
Organic superconductors: structural aspects and design of new materials Williams, Jack M.; Beno, Mark A.; Wang, Hau H. Accounts of Chemical Research, Vol. 18, Issue 9 https://doi.org/10.1021/ar00117a001	journal	September 1985
Superconductivity at 18 K in potassium-doped C60 Hebard, A. F.; Rosseinsky, M. J.; Haddon, R. C. Nature, Vol. 350, Issue 6319 https://doi.org/10.1038/350600a0	journal	April 1991
Optical Dedoping Mechanism for P3HT:F4TCNQ Mixtures Fuzell, Jack; Jacobs, Ian E.; Ackling, Sophia The Journal of Physical Chemistry Letters, Vol. 7, Issue 21 https://doi.org/10.1021/acs.jpclett.6b02048	journal	October 2016
Stability of Charge Transfer States in F ₄ TCNQ-Doped P3HT Watts, Kristen E.; Neelamraju, Bharati; Ratcliff, Erin L. Chemistry of Materials, Vol. 31, Issue 17 https://doi.org/10.1021/acs.chemmater.9b01549	journal	December 2018
Spectral Signatures and Spatial Coherence of Bound and Unbound Polarons in P3HT Films: Theory Versus Experiment Ghosh, Raja; Chew, Annabel R.; Onorato, Jonathan The Journal of Physical Chemistry C, Vol. 122, Issue 31 https://doi.org/10.1021/acs.jpcc.8b03873	journal	July 2018
Dopant-Induced Ordering of Amorphous Regions in Regiorandom P3HT Yee, Patrick Y.; Scholes, D. Tyler; Schwartz, Benjamin J. The Journal of Physical Chemistry Letters, Vol. 10, Issue 17 https://doi.org/10.1021/acs.jpclett.9b02070	journal	August 2019
Designing Conjugated Polymers for Molecular Doping: The Roles of Crystallinity, Swelling, and Conductivity in Sequentially-Doped Selenophene-Based Copolymers Scholes, D. Tyler; Yee, Patrick Y.; McKeown, George R. Chemistry of Materials, Vol. 31, Issue 1 https://doi.org/10.1021/acs.chemmater.8b02648	journal	November 2018
Dodecaborane‐Based Dopants Designed to Shield Anion Electrostatics Lead to Increased Carrier Mobility in a Doped Conjugated Polymer Aubry, Taylor J.; Axtell, Jonathan C.; Basile, Victoria M. Advanced Materials, Vol. 31, Issue 11 https://doi.org/10.1002/adma.201805647	journal	January 2019
Correlation of Coexistent Charge Transfer States in F ₄ TCNQ-Doped P3HT with Microstructure Neelamraju, Bharati; Watts, Kristen E.; Pemberton, Jeanne E. The Journal of Physical Chemistry Letters, Vol. 9, Issue 23 https://doi.org/10.1021/acs.jpclett.8b03104	journal	November 2018
Charge–transfer organic crystals: Molecular vibrations and spectroscopic effects of electron–molecular vibration coupling of the strong electron acceptor TCNQF ₄ Meneghetti, Moreno; Pecile, Cesare The Journal of Chemical Physics, Vol. 84, Issue 8 https://doi.org/10.1063/1.450086	journal	April 1986
Structural and optical investigations of charge transfer complexes involving the F4TCNQ dianion Sutton, Ashley L.; Abrahams, Brendan F.; D'Alessandro, Deanna M. CrystEngComm, Vol. 16, Issue 24 https://doi.org/10.1039/c4ce00289j	journal	January 2014
Excited States in Electron-Transfer Reaction Products: Ultrafast Relaxation Dynamics of an Isolated Acceptor Radical Anion Horke, Daniel A.; Roberts, Gareth M.; Verlet, Jan R. R. The Journal of Physical Chemistry A, Vol. 115, Issue 30 https://doi.org/10.1021/jp2038202	journal	August 2011
Dianions of 7,7,8,8-tetracyano-p-quinodimethane and perfluorinated tetracyanoquinodimethane: Information on excited states from lifetime measurements in an electrostatic storage ring and optical absorption spectroscopy Panja, Subhasis; Kadhane, Umesh; Andersen, Jens Ulrik The Journal of Chemical Physics, Vol. 127, Issue 12 https://doi.org/10.1063/1.2771177	journal	September 2007
Single photon triggered dianion formation in TCNQ and F4TCNQ crystals Ma, Lin; Hu, Peng; Jiang, Hui Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep28510	journal	June 2016
Efficient molecular doping of polymeric semiconductors driven by anion exchange Yamashita, Yu; Tsurumi, Junto; Ohno, Masahiro Nature, Vol. 572, Issue 7771 https://doi.org/10.1038/s41586-019-1504-9	journal	August 2019
Bound-Excited Electronic States of the Anion of 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane Sobczyk, Monika; Skurski, Piotr; Simons, Jack The Journal of Physical Chemistry A, Vol. 107, Issue 37 https://doi.org/10.1021/jp0222999	journal	April 2003
Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion Roberts, Gareth M.; Lecointre, Julien; Horke, Daniel A. Physical Chemistry Chemical Physics, Vol. 12, Issue 23 https://doi.org/10.1039/c001438a	journal	January 2010
Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor Horke, Daniel A.; Li, Quansong; Blancafort, Lluís Nature Chemistry, Vol. 5, Issue 8 https://doi.org/10.1038/nchem.1705	journal	July 2013
Ultrafast spectroscopic characterization of 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its radical anion (TCNQ−) Ma, Lin; Hu, Peng; Kloc, Christian Chemical Physics Letters, Vol. 609 https://doi.org/10.1016/j.cplett.2014.06.029	journal	August 2014
Arbitrary-Order Density Functional Response Theory from Automatic Differentiation Ekström, Ulf; Visscher, Lucas; Bast, Radovan Journal of Chemical Theory and Computation, Vol. 6, Issue 7 https://doi.org/10.1021/ct100117s	journal	May 2010
Software update: the ORCA program system, version 4.0: Software update Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 1 https://doi.org/10.1002/wcms.1327	journal	July 2017
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Fully optimized contracted Gaussian basis sets for atoms Li to Kr Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 97, Issue 4 https://doi.org/10.1063/1.463096	journal	August 1992
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
Structural and Solvent Control of Nonadiabatic Photochemical Bond Formation: Photocyclization of o -Terphenyl in Solution Molloy, Molly S.; Snyder, Joshua A.; Bragg, Arthur E. The Journal of Physical Chemistry A, Vol. 118, Issue 22 https://doi.org/10.1021/jp501988g	journal	May 2014
Structural Heterogeneity in the Localized Excited States of Poly(3-hexylthiophene) Yu, Wenjian; Magnanelli, Timothy J.; Zhou, Jiawang The Journal of Physical Chemistry B, Vol. 120, Issue 22 https://doi.org/10.1021/acs.jpcb.6b04215	journal	May 2016
Solvent Tuning of a Conical Intersection: Direct Experimental Verification of a Theoretical Prediction Kahan, Anat; Wand, Amir; Ruhman, Sanford The Journal of Physical Chemistry A, Vol. 115, Issue 40 https://doi.org/10.1021/jp206412h	journal	October 2011
Reaction dynamics of excited radical ions revealed by femtosecond laser flash photolysis Fujitsuka, Mamoru; Majima, Tetsuro Journal of Photochemistry and Photobiology C: Photochemistry Reviews, Vol. 35 https://doi.org/10.1016/j.jphotochemrev.2017.12.003	journal	June 2018
Excited Doublet States of Electrochemically Generated Aromatic Imide and Diimide Radical Anions Gosztola, David; Niemczyk, Mark P.; Svec, Walter The Journal of Physical Chemistry A, Vol. 104, Issue 28 https://doi.org/10.1021/jp000706f	journal	July 2000
Dual electron transfer pathways from the excited C ₆₀ radical anion: enhanced reactivities due to the photoexcitation of reaction intermediates Fujitsuka, Mamoru; Ohsaka, Tatsuya; Majima, Tetsuro Physical Chemistry Chemical Physics, Vol. 17, Issue 46 https://doi.org/10.1039/C5CP05254H	journal	January 2015
Excited-State Properties of Radical Anions of C ₇₀ and Its Derivatives: Significant Differences from the Case of C ₆₀ Lu, Chao; Fujitsuka, Mamoru; Sugimoto, Akira The Journal of Physical Chemistry C, Vol. 122, Issue 25 https://doi.org/10.1021/acs.jpcc.7b10926	journal	December 2017
Excited-State Behavior of Thermally Stable Radical Ions Breslin, David T.; Fox, Marye Anne The Journal of Physical Chemistry, Vol. 98, Issue 2 https://doi.org/10.1021/j100053a011	journal	January 1994
Charge Transfer in Molecular Complexes with 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F ₄ -TCNQ): A Density Functional Theory Study Zhu, Lingyun; Kim, Eung-Gun; Yi, Yuanping Chemistry of Materials, Vol. 23, Issue 23 https://doi.org/10.1021/cm201798x	journal	December 2011
Degree of Charge Transfer in Donor–Acceptor Systems of the π–π Type Kampar, E.; Neilands, O. Russian Chemical Reviews, Vol. 55, Issue 4 https://doi.org/10.1070/RC1986v055n04ABEH003193	journal	April 1986

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
F4TCNQ
charge transfer complex
phenylenediamine
excited states

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Title: Spectroscopic Studies of Charge-Transfer Character and Photoresponses of F₄TCNQ-Based Donor–Acceptor Complexes