RESUMEN
Organic cocrystals, which are assembled by noncovalent intermolecular interactions, have garnered intense interest due to their remarkable chemicophysical properties and practical applications. One notable feature, namely, the charge transfer (CT) interactions within the cocrystals, not only facilitates the formation of an ordered supramolecular network but also endows them with desirable semiconductor characteristics. Here, we present the intriguing ambipolar CT properties exhibited by nanosheets composed of single cocrystals of C70/ferrocene (C70/Fc). When heated to 150 °C, the initially ambipolar monoclinic C70/Fc nanosheet-based field-effect transistors (FETs) were transformed into n-type face-centered cubic (fcc) C70 nanosheet-based FETs owing to the elimination of Fc. This thermally induced alteration in the crystal structure was accompanied by an irreversible switching of the semiconducting behavior of the device; thus, the device transitions from ambipolar to unipolar. Importantly, the C70/Fc nanosheet-based FETs were also found to be much more thermally stable than the previously reported C60/Fc nanosheet-based FETs. Furthermore, we conducted visible/near-infrared diffuse reflectance and photoemission yield spectroscopies to investigate the crucial role played by Fc in modulating the CT characteristics. This study provides valuable insights into the overall functionality of these nanosheet structures.
RESUMEN
In recent years, supramolecular cocrystals containing organic donors and acceptors have been explored as active components in organic field-effect transistors (FETs). Herein, we report the synthesis of novel single-cocrystal nanoribbons with ambipolar charge transport characteristics from C70 and 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin (3,5-TPP) in a 3 : 2 ratio. The C70/3,5-TPP nanoribbons exhibited a new strong absorption band in the near-infrared region, indicating the presence of charge-transfer interactions between C70 and 3,5-TPP in the cocrystals. We elucidated the mechanism of the charge-transport properties of the nanoribbons using photoemission yield spectroscopy in air and theoretical calculations. A strong interaction between porphyrins in the one-dimensional porphyrin chains formed in C70/3,5-TPP nanoribbons, which was confirmed by single-crystal X-ray diffraction, plays a crucial role in their hole transport properties.
RESUMEN
Recently, organic donor-acceptor (D-A) cocrystals have attracted special interest as functional materials because of their unique chemical and physical properties that are not exhibited by simple mixtures of their components. Herein, we report the preparation of one-dimensional novel D-A cocrystals from C60 and 5,10,15,20-tetrakis(3,5-dimethoxyphenyl)porphyrin (3,5-TPP); these cocrystals have near-infrared (NIR) light-sensing abilities, despite each of their component molecule individually having no NIR light-sensing properties. Micrometer-sized rectangular columnar C60-3,5-TPP cocrystals were produced by a simple liquid-liquid interfacial precipitation method. The cocrystals exhibit a new strong transition in the NIR region indicative of the existence of charge-transfer interactions between C60 and 3,5-TPP in the cocrystals. The C60-3,5-TPP cocrystals showed n-type transport characteristics with NIR light-sensing properties when the cocrystals were incorporated in bottom-gate/bottom-contact organic phototransistors, revealing that organic cocrystals with suitable charge-transfer interaction are useful as functional materials for the creation of novel NIR-light-sensing devices.