We designed and synthesized a novel di(benz[f ]indenone)-fused tetraazaanthracene derivative and isolated its two isomers, 1a and 1s, having anti and syn configurations, respectively. Their structure and that of the condensation reaction intermediates, anti-2a and syn-2s, were fully characterized using one-and twodimensional nuclear magnetic resonance spectroscopy and singlecrystal X-ray diffraction. The optical and electronic properties of 1a and 1s were investigated using ultraviolet−visible absorption and fluorescence spectroscopies, cyclic voltammetry, and time-dependent density functional theory calculations. The presence of the carbonyl and ethynyltris(isopropyl)silane groups endows the di(benzoindenone)-fused azaacene derivatives with a strong electron accepting character. With an electron affinity of approximately −3.7 eV, the two isomers represent attractive electron-deficient molecular systems for the generation of n-channel semiconducting materials. Organic field effect transistors of 1a and 1s showed electron transport, and organic solar cells gave a proof of concept of the potential of the two compounds as electron acceptor materials when they are paired with an electron donor polymer.

The fabrication of high quality nanophotonic surfaces for integration in optoelectronic devices remains a challenge because of the complexity and cost of top–down nanofabrication strategies. Combining colloidal synthesis with templated self‐assembly emerged as an appealing low‐cost solution. However, it still faces several obstacles before integration in devices can become a reality. This is mostly due to the difficulty in assembling small nanoparticles (<50 nm) in complex nanopatterns with a high yield. In this study, a reliable methodology is proposed to fabricate printable nanopatterns with an aspect ratio varying from 1 to 10 and a lateral resolution of 30 nm via nanocube assembly and epitaxy. Investigating templated assembly via capillary forces, a new regime was identified that was used to assemble 30–40 nm nanocubes in a patterned polydimethylsiloxane template with a high yield for both Au and Ag with multiple particles per trap. This new method relies on the generation and control of an accumulation zone at the contact line that is thin as opposed to dense, displaying higher versatility. This is in contrast with conventional wisdom, identifying a dense accumulation zone as a requirement for high‐yield assembly. In addition, different formulations are proposed that can be used for the colloidal dispersion, showing that the standard water‐surfactant solutions can be replaced by surfactant‐free ethanol solutions, with good assembly yield. This allows to minimize the presence of surfactants that can affect electronic properties. Finally, it is shown that the obtained nanocube arrays can be transformed into continuous monocrystalline nanopatterns via nanocube epitaxy at near ambient temperature, and transferred to different substrates via contact printing. This approach opens new doors to the templated assembly of small colloids and could find potential applications in various optoelectronic devices ranging from solar cells to light‐emitting diodes and displays.