Mori Sakura, Moles Quintero Sergio, Tabaka Naoki, Kishi Ryohei, González Núñez Raúl, Harbuzaru Alexandra, Ponce Ortiz Rocío, Marín-Beloqui Jose, Suzuki Shuichi, Kitamura Chitoshi, Gómez-García Carlos J, Dai Yasi, Negri Fabrizia, Nakano Masayoshi, Kato Shin-Ichiro, Casado Juan
Department of Materials Science, School of Engineering, The University of Shiga Prefecture, 2500 Hassaka-cho, Hikone, Shiga, 522-8533, Japan.
Department of Physical Chemistry, University of Málaga, Andalucia-Tech Campus de Teatinos s/n, 29071, Málaga, Spain.
Angew Chem Int Ed Engl. 2022 Aug 15;61(33):e202206680. doi: 10.1002/anie.202206680. Epub 2022 Jul 4.
Four difluorenoheteroles having a central quinoidal core with the heteroring varying as furan, thiophene, its dioxide derivative and pyrrole have shown to be medium character diradicals. Solid-state structures, optical, photophysical, magnetic, and electrochemical properties have been discussed in terms of diradical character, variation of aromatic character and captodative effects (electron affinity). Organic field-effect transistors (OFETs) have been prepared, showing balanced hole and electron mobilities of the order of 10 cm V s or ambipolar charge transport which is first inferred from their redox amphoterism. Quantum chemical calculations show that the electrical behavior is originated from the medium diradical character which produces similar reorganization energies for hole and electron transports. The vision of a diradical as simultaneously bearing pseudo-hole and pseudo-electron defects might justify the reduced values of reorganization energies for both regimes. Structure-function relationships between diradical and ambipolar electrical behavior are revealed.
四种具有中心醌型核心的二芴杂环化合物，其杂环分别为呋喃、噻吩、其二氧化物衍生物和吡咯，已被证明是中等性质的双自由基。从双自由基特性、芳香性变化和俘精酸酐效应（电子亲和力）方面讨论了固态结构、光学、光物理、磁性和电化学性质。制备了有机场效应晶体管（OFET），显示出平衡的空穴和电子迁移率，约为10 cm² V⁻¹ s⁻¹，或者从其氧化还原两性推断出的双极性电荷传输。量子化学计算表明，电学行为源于中等双自由基特性，该特性为空穴和电子传输产生相似的重组能。将双自由基视为同时带有准空穴和准电子缺陷的观点，可能解释了两种情况下重组能降低的值。揭示了双自由基与双极性电学行为之间的结构-功能关系。
