Theoretical Study on Charge Transport Properties of a Series of

doi:10.1007/s40242-025-5176-8

Abstract

Abstract: Linear fused acenes exhibit excellent charge transport properties but suffer from poor solubility and stability. This study investigates "H-type" acene derivatives to address the poor solubility and stability of linear acenes by Marcus theory and kinetic Monte Carlo simulations. The findings reveal that "H-type" conjugation enhances photostability, oxidative stability, and solubility compared to linear acenes, with series a exhibiting superior solubility. The reorganization energy decreases with molecular extension, following trends similar to linear acenes. Key electronic structure differences were identified: thiophene substitution (series b) localizes the highest occupied molecular orbital (HOMO) on the bridging carbon atoms, while benzene substitution (series a) localizes it on the central acene core. Crucially, a strong correlation is established between the molecular structure parameter |ΔR| and crystal packing modes: |ΔR|<0.7 yields 1D/2D stacking; 0.7<|ΔR|<1.1 produces herringbone packing; and |ΔR|>1.1 leads to beneficial pitched π-stacking. Mobility calculations showed benzene-extended derivatives exhibit strong anisotropy. Thiophene expansion (b-3) reduces anisotropy, and benzothiophene (b-3*) improves the anisotropic mobility of molecules. This is attributed to favorable S···C interactions that suppress detrimental molecular slip. These results provide a critical theoretical framework for future development of "H-type" acene materials.

Key words: Acene derivative, Charge transport, Molecular stacking

SUN Xiaoqi, WANG Jin, JIN Hengyu, ZHAO Qi, GUO Jingfu, REN Ai-Min. Theoretical Study on Charge Transport Properties of a Series of "H-type" Acene Derivatives[J]. Chemical Research in Chinese Universities, 2025, 41(5): 1157-1172.

References

[1] Bibi A., Turan O., J. Mater. Chem. C, 2025, 13, 8354.
[2] Yang N., Zhang S., Cui Y., Wang J., Cheng S., Hou J., Nat. Rev. Mater., 2025, 10, 404.
[3] Nithyamol M., Acchutharaman K. R., Aravinth K., Balaji Bhargav P., Prog. Org. Coat, 2025, 209, 109594.
[4] Xie X. Y., Liu D., Zhao Z. N., Gao C., Wang P., Jiang C. X., Liu X. F., Zhang X. T., Ren Z. J., Yan X. K., Hu W. P., Dong H. L., Angew. Chem. Int. Ed., 2024, 136, e202319380.
[5] Okamoto T., Yu C. P., Mitsui C., Yamagishi M., Ishii H., Takeya J., J. Am. Chem. Soc., 2020, 20, 9083.
[6] Payne M. M., Parkin S. R., Anthony J. E., Kuo C.-C.Jackson T. N., J. Am. Chem. Soc., 2005, 14, 4986.
[7] Mondal R., Tönshoff C., Khon D., Neckers D. C., Bettinger H. F., J. Am. Chem. Soc., 2009, 131,14281.
[8] Biermann D., Schmidt W., J. Am. Chem. Soc., 1980, 102, 3173.
[9] Fatayer S., Albrecht F., Zhang Y., Urbonas D., Peña D., Moll N., Gross L., Science, 2019, 365, 142.
[10] Kaur I., Jazdzyk M., Stein N. N., Prusevich P., Miller G. P., J. Am. Chem. Soc., 2010, 132, 1261.
[11] Anthony J. E., Angew. Chem. Int. Ed., 2010, 47, 425.
[12] Stępień M., Gońka E., Żyła M.Sprutta N., Chem. Rev., 2017, 117, 3479.
[13] Yamaguchi Y., Kojiguchi Y., Kawata S., Mori T., Okamoto K., Tsutsui M., Koganezawa T., Katagiri H.Yasuda T., Chem. Mater., 2020, 32, 5350.
[14] Kotwica K., Wielgus I., Proń A., Materials, 2021, 14, 5155.
[15] Yamaguchi Y., Kojiguchi Y., Kawata S., Mori T., Okamoto K., Tsutsui M., Koganezawa T., Katagiri H., Yasuda T., Angew. Chem. Int. Ed., 2019, 58, 10708.
[16] Huang W., Xie W., Huang H., Zhang H., Liu H., J. Phys. Chem. Lett., 2020, 11, 4548.
[17] Benny A., Sasikumar D., Hariharan M., J. Phys. Chem. C, 2019, 123, 26758.
[18] Clar E., Kelly W., Niven W. G., Chem. Soc., 1956, 1833.
[19] Herbstein F. H., Acta Crystallographica Section B, 1979, 35, 1661.
[20] Hatakeyama T., Hashimoto S., Seki S., Nakamura M., J. Am. Chem. Soc., 2011, 133, 18614.
[21] Ueda Y., Tsuji H., Tanaka H., Nakamura E., Chem-Asian J., 2014, 9, 1623.
[22] Huang D.-C., Kuo C.-H., Ho M.-T., Lin B.-C., Peng W.-T., Chao I., Hsu C.-P., Tao Y.-T., J. Mater. Chem. C, 2017, 31, 7935.
[23] Kumar S., Huang D.-C., Venkateswarlu S., Tao Y.-T., J. Org. Chem., 2018, 83, 11614.
[24] Tian D., Ma Z., Gu L., Zhou C., Li C., Wang Z., Wang H., Crystal Growth & Design, 2020, 20, 4479.
[25] Xie Y., Fujimoto T., Dalgleish S., Shuku Y., Matsushita M. M., Awaga K., J. Mater. Chem. C, 2013, 21, 3467.
[26] Takimiya K., Yamamoto T., Ebata H., Izawa T., Sci. Technol. Adv. Mater., 2007, 4, 273.
[27] Fischer E., Larsen J., Christensen J. B., Fourmigué M., Madsen H. G., Harrit N., J. Org. Chem., 1996, 61, 6997.
[28] Yamamoto A., Ohta E., Kishigami N., Tsukahara N., Tomiyori Y., Sato H., Matsui Y., Kano Y., Mizuno K., Ikeda H., Tetrahedron Letters, 2013, 31, 4049.
[29] Zheng X., Su R., Wang Z., Wang T., Bin Z., She Z., Gao G., You J., Org. Lett., 2019, 21, 797.
[30] Brusso J. L., Hirst O. D., Dadvand A., Ganesan S., Cicoira F., Robertson C. M., Oakley R. T., Rosei F., Perepichka D. F., Chem. Mater., 2008, 20, 2484.
[31] Fan H., Zou S., Gao J., Chen R., Ma Q., Ma W., Zhang H., Chen G., Huo X., Liu Z., Dang Y., Hu W., J. Mater. Chem. C, 2020, 8, 11477.
[32] Cui X., Xiao C., Winands T., Koch T., Li Y., Zhang L., Doltsinis N. L., Wang Z., J. Am. Chem. Soc., 2018, 38, 12175.
[33] Watanabe M., Chang Y. J., Liu S.-W., Chao T.-H., Goto K., Islam M. M., Yuan C.-H., Tao Y.-T., Shinmyozu T., Chow T. J., Nature Chem., 2012, 4, 574.
[34] Zhang S.-F., Chen X.-K., Fan J.-X., Ren A.-M., Org. Electron, 2013, 14, 607.
[35] Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Scalmani G., Barone V., Mennucci B., Petersson G. A., Nakatsuji H., Caricato M., Li X., Hratchian H. P., Izmaylov A. F., Bloino J., Zheng G., Sonnenberg J. L., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Nakai H., Vreven T., Montgomery J. A., Jr, Peralta J. E., Ogliaro F., Bearpark M., Heyd J. J., Brothers E., Kudin K. N., Staroverov V. N., Kobayashi R., Normand J., Raghavachari K., Rendell A., Burant J. C., Iyengar S. S., Tomasi J., Cossi M., Rega N., Millam J. M., Klene M., Knox J. E., Cross J. B., Bakken V., Adamo C., Jaramillo J., Gomperts R., Stratmann R. E., Yazyev O., Austin A. J., Cammi R., Pomelli C., Ochterski J. W., Martin R. L., Morokuma K., Zakrzewski V. G., Voth G. A., Salvador P., Dannenberg J. J., Dapprich S., Daniels A. D., Farkas Ö., Foresman J. B., Ortiz J. V., Cioslowski J., Fox D. J., Gaussian 09 (Revision D), Gaussian, Inc., Wallingford CT, 2013.
[36] Zanith C. C., Pliego J. R., J. Comput. Aid. Mol. Des., 2015, 29, 217.
[37] Harald O., Karsten R., Jochen B., Chem. Rev., 2017,117, 10319.
[38] Fratini S., Mayou D., Ciuchi S., Adv. Funct. Mater., 2016, 26, 2292.
[39] Coropceanu V., Kwon O., Wex B., Kaafarani B. R., Gruhn N. E., Durivage J. C., Neckers D. C., Brédas J.-L., Chemistry, 2010, 12, 2073.
[40] Nan G., Yang X., Wang L., Shuai Z., Zhao Y., Phys. Rev. B, 2009, 79, 115203.
[41] Marcus R. A., Rev. Mod. Phys., 1993, 65, 599.
[42] Valeev E. F., Coropceanu V., da Silva Filho D. A., Salman S., Brédas J.-L., J. Am. Chem. Soc., 2006, 128, 9882.
[43] Te Velde G., Bickelhaupt F. M., Baerends E. J., Fonseca Guerra C., van Gisbergen S. J. A., Snijders J. G., Ziegler T., Comput. Chem., 2001, 22, 931.
[44] Coropceanu V., Kwon O., Wex B., Kaafarani B. R., Gruhn N. E., Durivage J. C., Neckers D. C., Brédas J.-L., Chemistry, 2010, 12, 2073.
[45] Sun X. Q., Qin G. Y., Li H. Y., Jin H. Y., Wang R., Li H., Ren A. M., Guo J. F., J. Chem. Phys., 2023, 158, 174301.
[46] Reimers J. R., J. Chem. Phys., 2001, 115, 9103.
[47] Wolff. S. K., Grimwood. D. J., McKinnon. J. J., Turner. M. J., Jayatilaka. D., Spackman. M. A., CrystalExplorer 3.1, University of Western Australia, Perth, Australia, 2012.
[48] Turney J. M., Simmonett A. C., Parrish R. M., Hohenstein E. G., Evangelista F. A., Fermann J. T., Mintz B. J., Burns L. A., Wilke J. J., Abrams M. L., Russ N. J., Leininger M. L., Janssen C. L., Seidl E. T., Allen W. D., Schaefer H. F., King R. A., Valeev E. F., Sherrill C. D., Crawford T. D., Wires Comput. Mol. Sci., 2012, 4, 556.
[49] Wang C., Dong H., Jiang L., Hu W., Chem. Soc. Rev., 2018, 47, 422.
[50] Sun X. Q., Qin G. Y., Li H. Y., Jin H. Y., Wang R., Li H., Ren A. M., Guo J. F., J. Chem. Phys., 2023, 158.
[51] Lin P.-P., Zhang S.-F., Zhang N.-X., Fan J.-X., Ji L.-F., Guo J.-F., Ren A.-M., Phys. Chem. Chem. Phys., 2019, 21, 3044.
[52] Duarte Ramos Matos G., Kyu D. Y., Loeffler H. H., Chodera J. D., Shirts M. R., Mobley D. L., J. Chem. Eng. Data, 2017, 62, 1559.
[53] Brédas J.-L., Beljonne D., Coropceanu V., Cornil J., Chem. Rev., 2004, 104, 4971.
[54] Takimiya K., Shinamura S., Osaka I., Miyazaki E., Adv. Mater., 2012, 23, 4347.
[55] Lu T., Chen F., J. Comput. Chem., 2012, 33, 580.
[56] Lee N.-E., Zhou J.-J., Agapito L. A., Bernardi M., Phys. Rev. B, 2018, 97, 115203.
[57] Karl N., Marktanner J., Mol. Cryst. Liq. Cryst., 2001, 355, 149.
[58] Goldmann C., Haas S., Krellner C., Pernstich K., Gundlach D., Batlogg B., J. Appl. Phys., 2004, 96, 2080.
[59] Jurchescu O. D., Baas J., Palstra T. M., J. Appl. Phys., 2004, 84, 3061.

Theoretical Study on Charge Transport Properties of a Series of "H-type" Acene Derivatives

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