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Characterization of Furan- and Thiophene-Containing Bispyridyl Oligomers via Spectroscopic, Electrochemical, and TD-DFT Methods

Cite this: J. Phys. Chem. C 2019, 123, 24, 15176–15185
Publication Date (Web):May 22, 2019
Copyright © 2019 American Chemical Society

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    Abstract Image

    The study of π-conjugated oligomers has garnered significant interest because of their use in organic optoelectronic devices, such as organic light-emitting diodes or organic field-effect transistors. Herein, we varied the inner heterocyclic units of pyridyl (Pyr)-capped π-conjugated oligomers consisting of furan (F) and thiophene (T) subunits to afford homomeric (Pyr2F3 and Pyr2T3) and heteromeric (Pyr2F2T and Pyr2T2F) molecules as applicable semiconducting building blocks. The oligomers were synthesized, and their solution- and solid-state spectroscopic properties were characterized. Compared to their thiophene congeners, oligomers with furans directly attached to the pyridyl moieties (Pyr2F3 and Pyr2F2T) gave rise to larger solution-state quantum yields and optical band gaps. Oligomers possessing a central furan subunit (Pyr2F3 and Pyr2T2F), on the other hand, were found to be nearly nonemissive in the solid state, which is attributed to nonradiative decay likely caused by π–π stacking interactions. Unlike the Pyr2T2F hybrid oligomer, Pyr2F2T exhibited not only a comparatively high solution-state quantum yield (7%) but also the brightest solid-state quantum yield emission (5%) and photostability (98%) when evaluated under ambient conditions. Density functional theory (DFT) computations support these trends, indicating that the largest HOMO–LUMO energy gaps and optical band gaps are possessed by Pyr2F3 and Pyr2F2T while those of Pyr2T2F and Pyr2T3 are the lowest among the oligomers considered here (i.e., Pyr2F3 > Pyr2F2T > Pyr2T2F > Pyr2T3). These results suggest that hybrid furan–thiophene oligomers—like that of Pyr2F2T—could serve as viable building blocks for optoelectronic devices, while possessing the positive attributes of both individual heterocycles in a synergistic manner.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.9b01510.

    • General information, synthesis procedures, structure refinement and computational details, CV, fluorescence lifetime decay curves and exponential decay fits, NMR spectra, and mass spectrometry analysis reports (PDF)

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    Cited By

    This article is cited by 10 publications.

    1. Morgan A. Perkins, Laura M. Cline, Gregory S. Tschumper. Torsional Profiles of Thiophene and Furan Oligomers: Probing the Effects of Heterogeneity and Chain Length. The Journal of Physical Chemistry A 2021, 125 (28) , 6228-6237.
    2. Lu Chen, Jicheng Yi, Ruijie Ma, Lu Ding, Top Archie Dela Peña, Heng Liu, Jian Chen, Cuifen Zhang, Chaoyue Zhao, Wen Lu, Qi Wei, Bin Zhao, Huawei Hu, Jiaying Wu, Zaifei Ma, Xinhui Lu, Mingjie Li, Guangye Zhang, Gang Li, He Yan. An Isomeric Solid Additive Enables High‐Efficiency Polymer Solar Cells Developed Using a Benzo‐Difuran‐Based Donor Polymer. Advanced Materials 2023, 35 (26)
    3. Charlotte Mallet, Pierre Frère. Furylenevinylene Oligomers as Extended Conjugated Systems from Renewable Materials. European Journal of Organic Chemistry 2022, 2022 (47)
    4. Jonas Bachmann, Andreas Helbig, Merian Crumbach, Ivo Krummenacher, Holger Braunschweig, Holger Helten. Fusion of Aza‐ and Oxadiborepins with Furans in a Reversible Ring‐Opening Process Furnishes Versatile Building Blocks for Extended π‐Conjugated Materials. Chemistry – A European Journal 2022, 28 (63)
    5. Jicheng Yi, Mingao Pan, Lu Chen, Yuzhong Chen, Indunil Chathurangani Angunawela, Siwei Luo, Ting Zhang, Anping Zeng, Jian Chen, Zhenyu Qi, Han Yu, Wei Liu, Joshua Yuk Lin Lai, Ha Kyung Kim, Xunjin Zhu, Harald Ade, Haoran Lin, He Yan. A Benzo[1,2‐b:4,5‐b′]Difuran Based Donor Polymer Achieving High‐Performance (>17%) Single‐Junction Organic Solar Cells with a Fill Factor of 80.4%. Advanced Energy Materials 2022, 12 (33)
    6. Dilan Karunathilaka, R. M. G. Rajapakse, April E. Hardin, Thomas More Sexton, Nicholas E. Sparks, Jacquelyn J. Mosely, Arnold L. Rheingold, Nathan I. Hammer, Gregory S. Tschumper, Davita L. Watkins. Correlation of solid-state order to optoelectronic behavior in heterocyclic oligomers. CrystEngComm 2022, 24 (25) , 4564-4572.
    7. V A Bastos, T J da Silva, M J Caldas. Thiophene–furan oligomers: beyond-DFT study of electronic and optical properties. Electronic Structure 2022, 4 (1) , 015004.
    8. Bing Zheng, Jianling Ni, Shaman Li, Yuchen Yue, Jingxia Wang, Jianqi Zhang, Yongfang Li, Lijun Huo. Conjugated Mesopolymer Achieving 15% Efficiency Single‐Junction Organic Solar Cells. Advanced Science 2022, 9 (8) , 2105430.
    9. Bing Zheng, Lijun Huo. Recent Advances of Furan and Its Derivatives Based Semiconductor Materials for Organic Photovoltaics. Small Methods 2021, 5 (9)
    10. Hardin, Ellington, Nguyen, Rheingold, Tschumper, Watkins, Hammer. A Raman Spectroscopic and Computational Study of New Aromatic Pyrimidine-Based Halogen Bond Acceptors. Inorganics 2019, 7 (10) , 119.

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