Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles

Fahidat A. Gbadamosi; Md Faizul Islam; Abdulla E. Shaker; Gamage Isuri P. Wijesekera; Mark D. Smith; J. S.Raaj Vellore Winfred; Shehani T. Wetthasinghe; Sophya Garashchuk; Andrew B. Greytak; Linda S. Shimizu

doi:10.1021/acs.jpcc.5c04522

Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles

Fahidat A. Gbadamosi, Md Faizul Islam, Abdulla E. Shaker, Gamage Isuri P. Wijesekera, Mark D. Smith, J. S.Raaj Vellore Winfred, Shehani T. Wetthasinghe, Sophya Garashchuk, Andrew B. Greytak, Linda S. Shimizu

Chemical Separations Group

Research output: Contribution to journal › Article › peer-review

Abstract

Achieving tunable electrical conductivity in organic materials is a key challenge for the development of next-generation semiconductors. This study demonstrates a novel approach using triphenylamine (TPA) bis-urea macrocycles as supramolecular hosts for guest-induced modulation of charge-transfer (CT) properties. By encapsulating guests with varying reduction potentials, including 2,5-dichloro-1,4-benzoquinone (ClBQ), 2,1,3-benzothiadiazole (BTD), and malononitrile (MN), we observed significant changes in the electrical conductivity. Crystals of the 1(ClBQ)_0.31complex exhibited an electrical conductivity of ∼2.08 × 10^–5S cm^–1, a 10,000-fold enhancement compared to the pristine host. This is attributed to efficient CT observed in spectroscopic analyses and is consistent with the computed small HOMO–LUMO gap (2.92 eV) in a model of the host–guest system. 1(MN)_0.39and 1(BTD)_0.5demonstrated moderate conductivities explained by the interplay of electronic coupling, reorganization energy, and energy gap. Lower ratios of guest inclusion decreased the electrical conductivity by 10-fold in 1(ClBQ)_0.18, while 1(MN)_0.25and 1(BTD)_0.41were nonconductive (10^–9S cm^–1). This work highlights the potential of metal-free, porous organic systems as tunable semiconductors, offering a pathway to innovative applications in organic electronics.

Original language	English
Pages (from-to)	15922-15931
Number of pages	10
Journal	Journal of Physical Chemistry C
Volume	129
Issue number	35
DOIs	https://doi.org/10.1021/acs.jpcc.5c04522
State	Published - Sep 4 2025

Funding

This work was supported in part by the National Science Foundation (NSF) CHE-2203830, OIA-1655740, CHE-2308922, and CNS-2320292. Transient absorption measurements were performed on a spectrometer supported by the National Science Foundation under Grant No. CHE-1919633. This research used resources provided by the Materials Characterization Laboratory at the FSU Department of Chemistry and Biochemistry (FSU075000MAC). Any opinions, findings, conclusions, or recommendations expressed in this material are those of the authors and do not necessarily reflect those of the NSF.

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10.1021/acs.jpcc.5c04522

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Gbadamosi, F. A., Islam, M. F., Shaker, A. E., Wijesekera, G. I. P., Smith, M. D., Winfred, J. S. R. V., Wetthasinghe, S. T., Garashchuk, S., Greytak, A. B., & Shimizu, L. S. (2025). Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles. Journal of Physical Chemistry C, 129(35), 15922-15931. https://doi.org/10.1021/acs.jpcc.5c04522

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title = "Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles",

abstract = "Achieving tunable electrical conductivity in organic materials is a key challenge for the development of next-generation semiconductors. This study demonstrates a novel approach using triphenylamine (TPA) bis-urea macrocycles as supramolecular hosts for guest-induced modulation of charge-transfer (CT) properties. By encapsulating guests with varying reduction potentials, including 2,5-dichloro-1,4-benzoquinone (ClBQ), 2,1,3-benzothiadiazole (BTD), and malononitrile (MN), we observed significant changes in the electrical conductivity. Crystals of the 1(ClBQ)0.31complex exhibited an electrical conductivity of ∼2.08 × 10–5S cm–1, a 10,000-fold enhancement compared to the pristine host. This is attributed to efficient CT observed in spectroscopic analyses and is consistent with the computed small HOMO–LUMO gap (2.92 eV) in a model of the host–guest system. 1(MN)0.39and 1(BTD)0.5demonstrated moderate conductivities explained by the interplay of electronic coupling, reorganization energy, and energy gap. Lower ratios of guest inclusion decreased the electrical conductivity by 10-fold in 1(ClBQ)0.18, while 1(MN)0.25and 1(BTD)0.41were nonconductive (10–9S cm–1). This work highlights the potential of metal-free, porous organic systems as tunable semiconductors, offering a pathway to innovative applications in organic electronics.",

author = "Gbadamosi, \{Fahidat A.\} and Islam, \{Md Faizul\} and Shaker, \{Abdulla E.\} and Wijesekera, \{Gamage Isuri P.\} and Smith, \{Mark D.\} and Winfred, \{J. S.Raaj Vellore\} and Wetthasinghe, \{Shehani T.\} and Sophya Garashchuk and Greytak, \{Andrew B.\} and Shimizu, \{Linda S.\}",

note = "Publisher Copyright: {\textcopyright} 2025 American Chemical Society",

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month = sep,

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doi = "10.1021/acs.jpcc.5c04522",

language = "English",

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Gbadamosi, FA, Islam, MF, Shaker, AE, Wijesekera, GIP, Smith, MD, Winfred, JSRV, Wetthasinghe, ST, Garashchuk, S, Greytak, AB & Shimizu, LS 2025, 'Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles', Journal of Physical Chemistry C, vol. 129, no. 35, pp. 15922-15931. https://doi.org/10.1021/acs.jpcc.5c04522

TY - JOUR

T1 - Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles

AU - Gbadamosi, Fahidat A.

AU - Islam, Md Faizul

AU - Shaker, Abdulla E.

AU - Wijesekera, Gamage Isuri P.

AU - Smith, Mark D.

AU - Winfred, J. S.Raaj Vellore

AU - Wetthasinghe, Shehani T.

AU - Garashchuk, Sophya

AU - Greytak, Andrew B.

AU - Shimizu, Linda S.

PY - 2025/9/4

Y1 - 2025/9/4

N2 - Achieving tunable electrical conductivity in organic materials is a key challenge for the development of next-generation semiconductors. This study demonstrates a novel approach using triphenylamine (TPA) bis-urea macrocycles as supramolecular hosts for guest-induced modulation of charge-transfer (CT) properties. By encapsulating guests with varying reduction potentials, including 2,5-dichloro-1,4-benzoquinone (ClBQ), 2,1,3-benzothiadiazole (BTD), and malononitrile (MN), we observed significant changes in the electrical conductivity. Crystals of the 1(ClBQ)0.31complex exhibited an electrical conductivity of ∼2.08 × 10–5S cm–1, a 10,000-fold enhancement compared to the pristine host. This is attributed to efficient CT observed in spectroscopic analyses and is consistent with the computed small HOMO–LUMO gap (2.92 eV) in a model of the host–guest system. 1(MN)0.39and 1(BTD)0.5demonstrated moderate conductivities explained by the interplay of electronic coupling, reorganization energy, and energy gap. Lower ratios of guest inclusion decreased the electrical conductivity by 10-fold in 1(ClBQ)0.18, while 1(MN)0.25and 1(BTD)0.41were nonconductive (10–9S cm–1). This work highlights the potential of metal-free, porous organic systems as tunable semiconductors, offering a pathway to innovative applications in organic electronics.

AB - Achieving tunable electrical conductivity in organic materials is a key challenge for the development of next-generation semiconductors. This study demonstrates a novel approach using triphenylamine (TPA) bis-urea macrocycles as supramolecular hosts for guest-induced modulation of charge-transfer (CT) properties. By encapsulating guests with varying reduction potentials, including 2,5-dichloro-1,4-benzoquinone (ClBQ), 2,1,3-benzothiadiazole (BTD), and malononitrile (MN), we observed significant changes in the electrical conductivity. Crystals of the 1(ClBQ)0.31complex exhibited an electrical conductivity of ∼2.08 × 10–5S cm–1, a 10,000-fold enhancement compared to the pristine host. This is attributed to efficient CT observed in spectroscopic analyses and is consistent with the computed small HOMO–LUMO gap (2.92 eV) in a model of the host–guest system. 1(MN)0.39and 1(BTD)0.5demonstrated moderate conductivities explained by the interplay of electronic coupling, reorganization energy, and energy gap. Lower ratios of guest inclusion decreased the electrical conductivity by 10-fold in 1(ClBQ)0.18, while 1(MN)0.25and 1(BTD)0.41were nonconductive (10–9S cm–1). This work highlights the potential of metal-free, porous organic systems as tunable semiconductors, offering a pathway to innovative applications in organic electronics.

UR - https://www.scopus.com/pages/publications/105015376969

U2 - 10.1021/acs.jpcc.5c04522

DO - 10.1021/acs.jpcc.5c04522

M3 - Article

AN - SCOPUS:105015376969

SN - 1932-7447

VL - 129

SP - 15922

EP - 15931

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

IS - 35

ER -

Charge-Transfer-Driven Electrical Conductivity in Single Crystals of Assembled Triphenylamine Bis-urea Macrocycles

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