TY - JOUR
T1 - Excellent Semiconductors Based on Tetracenotetracene and Pentacenopentacene
T2 - From Stable Closed-Shell to Singlet Open-Shell
AU - Jousselin-Oba, Tanguy
AU - Mamada, Masashi
AU - Marrot, Jérôme
AU - Maignan, Antoine
AU - Adachi, Chihaya
AU - Yassar, Abderrahim
AU - Frigoli, Michel
N1 - Funding Information:
M.F. and A.Y. acknowledge financial support from the Agence Nationale de la Recherche ANR-16-CE07-0024 (GATE). T.J.-O. has been an International Research Fellow of the Japanese Society for the Promotion of Science (JSPS) for three months through the JSPS Summer Program and acknowledges CNRS for a Ph.D. grant. M.M. and C.A. acknowledge financial support from JST ERATO Grant No. JPMJER1305 and JSPS KAKENHI Grant No. JP19H02790. The authors thank Dr. W. J. Potscavage, Jr., for assistance in data processing.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/6/12
Y1 - 2019/6/12
N2 - Designing stable open-shell organic materials through the modifications of the π-topology of molecular organic semiconductors has recently attracted considerable attention. However, their uses as an active layer in organic field-effect transistors (OFETs) are very limited, and the obtained hole and electron charge mobilities are around 10-3 cm2 V-1 s-1. Herein, we disclose the synthesis of two peri-fused materials, so-called tetracenotetracene (TT) and pentacenopentacene (PP), which have low band gaps of 1.79 and 1.42 eV, respectively. Their ground state natures have been investigated by different experiments including steady state absorption, electron spin resonance, superconducting quantum interfering device, and variable-temperature NMR along with DFT calculations. TT and PP have closed-shell and singlet open-shell structures in their ground state, respectively, and possess high stability. Their biradical characteristics were found to be 0.50 and 0.64. The origin of the open-shell character of PP is related to the concomitant opening of two tetracenes with the recovering of two extra aromatic sextets and a small HOMO-LUMO energy gap (gap <1.5 eV). Thanks to the high stability, thin film OFET devices could be fabricated. In TG-BC configuration PP shows a remarkably high hole mobility of 1.4 cm2 V-1 s-1, while TT exhibits a hole mobility of 0.77 cm2 V-1 s-1. In the configuration of BG-TC, ambipolar behaviors for both were obtained with hole and electron mobilities of 0.21 and 0.01 cm2 V-1 s-1 for PP and 0.14 and 0.006 cm2 V-1 s-1 for TT.
AB - Designing stable open-shell organic materials through the modifications of the π-topology of molecular organic semiconductors has recently attracted considerable attention. However, their uses as an active layer in organic field-effect transistors (OFETs) are very limited, and the obtained hole and electron charge mobilities are around 10-3 cm2 V-1 s-1. Herein, we disclose the synthesis of two peri-fused materials, so-called tetracenotetracene (TT) and pentacenopentacene (PP), which have low band gaps of 1.79 and 1.42 eV, respectively. Their ground state natures have been investigated by different experiments including steady state absorption, electron spin resonance, superconducting quantum interfering device, and variable-temperature NMR along with DFT calculations. TT and PP have closed-shell and singlet open-shell structures in their ground state, respectively, and possess high stability. Their biradical characteristics were found to be 0.50 and 0.64. The origin of the open-shell character of PP is related to the concomitant opening of two tetracenes with the recovering of two extra aromatic sextets and a small HOMO-LUMO energy gap (gap <1.5 eV). Thanks to the high stability, thin film OFET devices could be fabricated. In TG-BC configuration PP shows a remarkably high hole mobility of 1.4 cm2 V-1 s-1, while TT exhibits a hole mobility of 0.77 cm2 V-1 s-1. In the configuration of BG-TC, ambipolar behaviors for both were obtained with hole and electron mobilities of 0.21 and 0.01 cm2 V-1 s-1 for PP and 0.14 and 0.006 cm2 V-1 s-1 for TT.
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U2 - 10.1021/jacs.9b03488
DO - 10.1021/jacs.9b03488
M3 - Article
C2 - 31117656
AN - SCOPUS:85066975060
SN - 0002-7863
VL - 141
SP - 9373
EP - 9381
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 23
ER -