TY - JOUR
T1 - Tuning the antiaromatic character and charge transport of pentalene-based antiaromatic compounds by substitution
AU - Wu, Jianglin
AU - Chen, Yao
AU - Liu, Jueshan
AU - Pang, Zhenguo
AU - Li, Guoping
AU - Lu, Zhiyun
AU - Huang, Yan
AU - Facchetti, Antonio
AU - Marks, Tobin J.
N1 - Funding Information:
We acknowledge the financial support for this work from the National Natural Science Foundation of China (project no. 21875148) (Y. H., Z. L., J. W., J. L.). T. M., A. F., and Y. C., J. W. are grateful to the Center for Light Energy Activated Redox Processes (LEAP), an Energy Frontier Research Center funded by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under award DE-SC0001059 (J. W.: fabricating device and other characterization, Y. C. and G. Li: materials synthesis, A. F. and T. J. M.: project advising), AFOSR grant FA9550-18-1-0320, the Flexterra Corporation, and the Office of Naval Research Contract N00014-20-1-2116. The use of the Advanced Photon Source, an Office of Science User Facility operated by the US DOE Office of Science by Argonne National Laboratory, was supported by the US DOE under contract DE-AC02-06CH11357. J. W. acknowledges the joint-PhD program supported by the China Scholarship Council (No. 201906240142) for a fellowship.
Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2022/2/21
Y1 - 2022/2/21
N2 - Understanding the structure-property relationships in antiaromatic molecules is crucial for controlling their electronic properties and designing new organic optoelectronic materials. Here we report the design, synthesis, and characterization of three new antiaromatic molecules (Pn, n = 1-4) based on the pentalene (P) antiaromatic core, to investigate how electron-donating and electron-accepting substituents affect P1-P4 properties. As expected, the optical, HOMO and LUMO energy levels and electronic structure are greatly modulated by core substitution. Compared to the unsubstituted compound (P1), P3 and P4 containing strong electron-withdrawing units reduced antiaromaticity as assessed by nucleus-independent chemical shift (NICS) calculations compared with P2, which is functionalized with strong electron-donating units, showing that substitution strongly tunes local antiaromaticity. Organic field-effect transistors (OFETs) fabricated using these materials indicate that P2 has an average hole mobility of ∼10-4 cm2 V-1 s-1 while P3 has an average electron mobility of up to 0.03 cm2 V-1 s-1, versus FET-inactive P1. Therefore, introduction of strong π-extended electron-withdrawing or electron-donating substituents onto an antiaromatic core is an effective strategy to switch-on charge transport capacity. This journal is
AB - Understanding the structure-property relationships in antiaromatic molecules is crucial for controlling their electronic properties and designing new organic optoelectronic materials. Here we report the design, synthesis, and characterization of three new antiaromatic molecules (Pn, n = 1-4) based on the pentalene (P) antiaromatic core, to investigate how electron-donating and electron-accepting substituents affect P1-P4 properties. As expected, the optical, HOMO and LUMO energy levels and electronic structure are greatly modulated by core substitution. Compared to the unsubstituted compound (P1), P3 and P4 containing strong electron-withdrawing units reduced antiaromaticity as assessed by nucleus-independent chemical shift (NICS) calculations compared with P2, which is functionalized with strong electron-donating units, showing that substitution strongly tunes local antiaromaticity. Organic field-effect transistors (OFETs) fabricated using these materials indicate that P2 has an average hole mobility of ∼10-4 cm2 V-1 s-1 while P3 has an average electron mobility of up to 0.03 cm2 V-1 s-1, versus FET-inactive P1. Therefore, introduction of strong π-extended electron-withdrawing or electron-donating substituents onto an antiaromatic core is an effective strategy to switch-on charge transport capacity. This journal is
UR - http://www.scopus.com/inward/record.url?scp=85123938478&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85123938478&partnerID=8YFLogxK
U2 - 10.1039/d1tc03156b
DO - 10.1039/d1tc03156b
M3 - Article
AN - SCOPUS:85123938478
VL - 10
SP - 2724
EP - 2731
JO - Journal of Materials Chemistry C
JF - Journal of Materials Chemistry C
SN - 2050-7526
IS - 7
ER -