Masha Aleksich

Abstract

Metal-organic chalcogenolate (MOCha) hybrid assemblies are a class of nanomaterials that contain one- or two- dimensional (1D, 2D) repeatable units of inorganic nanostructures that are electronically isolated by an associated organic ligand framework. The three archetypes of silver MOChas contain variable chalcogen atoms: mithrene (AgSePh), thiorene (AgSPh), and tethrene (AgTePh). Small molecule serial femtosecond X-ray diffraction (smSFX) is employed for the crystal structure determination of several thiorene-adjacent MOCHas. In this collaboration, crystal structures of silver butanethiolate (C4), silver hexanethiolate (C6), and silver nonanethiolate (C9) were determined. We show that an odd–even effect originates from the orientation of the terminal methyl group and its role in packing efficiency. In addition, thiorene underwent crystal functionalization with a methoxy group at the 2-, 3-, and 4- positions (2M, 3M, 4M), and a methyl ester at the 2- and 4- positions on the phenyl ring (2MMB, 4MMB). One-dimensional MOChas possess high emissive profiles in the UV-Vis range. In addition, the position of the FG in 3M and 2MMB indicates a “shattering” effect of the 2D sheets of the inorganic layer into electronically isolated 1D nanowires. Topological engineering of MOCha crystals is a tool to control the dimensionality from 2D to 1D, while smSFX is utilized to show the effect structural changes have on optoelectronic properties via crystal structure determination of microcrystalline MOChas.