Size and Quality Enhancement of 2D Semiconducting Metal-Organic Chalcogenolates by Amine Addition.

The use of two-dimensional (2D) materials in next-generation technologies is often limited by small lateral size and/or crystal defects. Here, we introduce a simple chemical strategy to improve the size and overall quality of 2D metal-organic chalcogenolates (MOCs), a new class of hybrid organic-inorganic 2D semiconductors that can exhibit in-plane anisotropy and blue luminescence. By inducing the formation of silver-amine complexes during a solution growth method, we increase the average size of silver phenylselenolate (AgSePh) microcrystals from <5 μm to >1 mm, while simultaneously extending the photoluminescence lifetime and suppressing mid-gap emission. Mechanistic studies using 77Se NMR suggest dual roles for the amine in promoting the formation of a key reactive intermediate and slowing down the final conversion to AgSePh. Finally, we show that amine addition is generalizable to the synthesis of other 2D MOCs, as demonstrated by the growth of single crystals of silver 4-methylphenylselenolate (AgSePhMe), a novel member of the 2D MOC family.