Photoredox catalysis and artificial photosynthesis have been recognized as two sustainable approaches to utilize solar energy for chemical reactions and energy storage. One of the unsolved challenges is the development of an affordable, robust light harvester that has a panchromatic absorption range and efficiently provides separated charges for the desired photochemistry. The most commonly employed molecular photosensitizers include the noble metal-based ruthenium and iridium complexes, synthetically challenging porphyrin derivatives, and expensive, functionalized polypyridine compounds. Here, we describe the development of copper(I) dyes supported by bis(arylimino)acenaphthene (Ar-BIAN) ligands, which can be synthesized in fewer than three steps from commercial reagents. The diamagnetic, homoleptic complexes have been characterized by a suite of spectroscopic and analytical methods and exhibit panchromatic light absorption extending to the near infrared (NIR) region. Remarkably, the crystal structure of the complex bearing an <i>ortho</i>-iodoarylimino substituent displays a unique, almost-planar, rhomboid geometry around the copper(I) center, for crystals isolated from two disparate solvent combinations. Density functional theory (DFT) calculations were performed to provide insights into the spectroscopic features and the unusual coordination sphere around the metal center, and allude to non-covalent interactions between the iodides and copper(I). Preliminary studies were conducted to explore the application of these copper photosensitizers in dye-sensitized solar cells.

Development of bis(arylimino)acenaphthene (BIAN) copper complexes as visible light harvesters for photovoltaic and artificial photosynthetic applications

251st National Meeting (2016)

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