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Scanning tunneling microscopy (STM) offers unparalleled sub-molecular resolution for visualizing surface-bound molecular assemblies. We developed a custom 3D-printed liquid cell that enabled stable, long-duration liquid-phase STM imaging of a metallocene dimer assembled on a highly oriented pyrolytic graphite (HOPG) substrate. High-resolution images revealed two distinct molecular packing structures. However, STM alone is difficult to pinpoint the detailed molecular arrangements, resonance Raman spectroscopy (RRS) was used to provide complementary information. Aided with density functional theory (DFT) calculated RRS, a cis conformer of the metallocene dimer was identified as the more probable form in both crystal and surface-bound states. These findings led to assemblies with cyclopentadienyl rings pointing towards the HOPG, and the carbonyl groups towards the water. This work demonstrates the synergistic power of integrating STM, RRS, and DFT in elucidating molecular assembling structures at the solid–liquid interface. 

Photochemistry of multifunctional aromatics like vanillin can depend strongly on wavelength, initial concentration, and ionic strength. Using several narrow-band LEDs we present wavelength resolved quantum yields for loss of vanillin.