The properties as well as solid‐state structures, singlet fission, and organic field‐effect transistor (OFET) performance of three tetrafluoropentacenes (1,4,8,11: 10, 1,4,9,10: 11, 2,3,9,10: 12) are compared herein. The novel compounds 10 and 11 were synthesized in high purity from the corresponding 6,13‐etheno‐bridged precursors by reaction with dimethyl 1,2,4,5‐tetrazine‐3,6‐dicarboxylate at elevated temperatures. Although most of the molecular properties of the compounds are similar, their chemical reactivity and crystal structures differ considerably. Isomer 10 undergoes the orbital symmetry forbidden thermal [4+4] dimerization, whereas 11 and 12 are much less reactive. The isomers 11 and 12 crystallize in a herringbone motif, but 10 prefers π–π stacking. Although the energy of the first electric dipole‐allowed optical transition varies only within 370 cm⁻¹ (0.05 eV) for the neutral compounds, this amounts to roughly 1600 cm⁻¹ (0.20 eV) for radical cations and 1300 cm⁻¹ (0.16 eV) for dications. Transient spectroscopy of films of 11 and 12 reveals singlet‐fission time constants (91±11, 73±3 fs, respectively) that are shorter than for pentacene (112±9 fs). OFET devices constructed from 11 and 12 show close to ideal thin‐film transistor (TFT) characteristics with electron mobilities of 2×10⁻³ and 6×10⁻² cm² V⁻¹ s⁻¹, respectively.

中文翻译：

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通过特定位置的取代来调节有机半导体的电子和固态结构：四氟戊烯的情况

性质以及固态结构，单峰裂变，和三个tetrafluoropentacenes（1,4,8,11有机场效应晶体管（OFET）性能：10，1,4,9,10：11，2,3- ，9,10：12）在此进行比较。通过与1,2,4,5-四嗪-3,6-二羧酸二甲酯在高温下反应，由相应的6,13-​​乙氧基桥接的前体以高纯度合成了新型化合物 10和11。尽管化合物的大多数分子性质相似，但它们的化学反应性和晶体结构却有很大差异。异构体10经历轨道对称，禁止热[4 + 4]二聚化，而异构体 11和1112的反应性小得多。异构体11和12以人字形结晶，但是10更喜欢π-π堆积。尽管中性化合物的第一个电偶极子允许的光跃迁的能量仅在370 cm ^-1（0.05 eV）范围内变化，但对于自由基阳离子而言大约为1600 cm ^-1（0.20 eV），而在1300 cm ^-1（0.16） eV）。11和12薄膜的瞬态光谱显示单峰裂变时间常数（分别为91±11、73±3 fs），比并五苯（112±9 fs）短。由11和12构成的OFET设备显示出接近理想的薄膜晶体管（TFT）特性，电子迁移率分别为2×10 ^-3和6×10 ^-2  cm ²  V ^-1  s ^-1。