Three Isomeric Dioctyl Derivatives of 2,7-Dithienyl[1]benzo-thieno[3,2-b][1]benzothiophene: Synthesis, Optical, Thermal, and Semiconductor Properties

Organic semiconductor materials are interesting due to their application in various organic electronics devices. [1]benzothieno[3,2-b][1]benzothiophene (BTBT) is a widely used building block for the creation of such materials. In this work, three novel solution-processable regioisomeric derivatives of BTBT-2,7-bis(3-octylthiophene-2-yl)BTBT (<b>1</b>), 2,7-bis(4-octylthiophene-2-yl)BTBT (<b>2</b>), and 2,7-bis(5-octylthiophene-2-yl)BTBT (<b>3</b>)-were synthesized and investigated. Their optoelectronic properties were characterized experimentally by ultraviolet-visible and fluorescence spectroscopy, time-resolved fluorimetry, and cyclic voltammetry and studied theoretically by Time-Dependent Density Functional Theory calculations. Their thermal properties were investigated by a thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, and in situ small-/wide-angle X-ray scattering measurements. It was shown that the introduction of alkyl substituents at different positions (3, 4, or 5) of thiophene moieties attached to a BTBT fragment significantly influences the optoelectronic properties, thermal stability, and phase behavior of the materials. Thin films of each compound were obtained by drop-casting, spin-coating and doctor blade techniques and used as active layers for organic field-effect transistors. All the OFETs exhibited p-channel characteristics under ambient conditions, while compound <b>3</b> showed the best electrical performance with a charge carrier mobility up to 1.1 cm²·V^-1s^-1 and current on/off ratio above 10⁷.