Bipolar Electrochemistry with Organic Single Crystals for Wireless Synthesis of Metal–Organic Janus Objects and Asymmetric Photovoltage Generation

Abstract

Bipolar electrochemistry has recently emerged as a very unique method to address conducting particles in a wireless manner. The technique is often applied to the fabrication of Janus particles; however the chemical nature of the bipolar electrode has been essentially limited to carbon- or metal-based materials. Here, we report for the first time the use of conducting organic single crystals as bipolar electrodes for the preparation of a new generation of Janus objects. Fabre and Bechgaard salts involving respectively tetrathia- and tetraselenafulvalene were selected for proof-of-concept experiments. Such an approach allows to preserve the integrity of these fragile substrates because it necessitates neither electronic wiring nor mechanical contact. The site-selective electrodeposition of copper is successfully achieved, leading thus to a new metal–organic Janus structure. Subsequently, asymmetric generation of photovoltage under illumination is achieved due to the anisotropic presence of copper, making this approach interesting for the design of novel hybrid objects with applications in organic electronics or photocatalysis.