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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.
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This content will become publicly available on April 24, 2026
Exploring the Surface Chemistry of Cobalt Porphyrin Complexed with Iodine Using Single Molecule Microscopy and Theory
Understanding the interactions between molecules on surfaces is crucial for advancing technologies in sensing, catalysis, and energy harvesting. In this study we explore the complex surface chemistry resulting from the interaction of Co(II)octaethylporphyrin (CoOEP) and iodine, I2, both in solution and at the phenyloctane/HOPG interface. In pursuit of this goal, we report results from electrochemistry, NMR and UV-Vis spectroscopy, X-ray crystallography, scanning tunneling microscopy (STM), and density functional theory (DFT). Both spectroscopic methods of analysis confirmed that at and above the stoichiometric ratio of one CoOEP to one I2 the reaction product was metal centered CoIII(OEP)I. X-ray crystallography verified that a single iodine is bonded to each cobalt ion in the triclinic, P-1 system. The surface chemistry of CoOEP and I2 is complicated and remarkably dependent on the iodine concentration. STM images of CoOEP and I2 in phenyloctane on highly oriented pyrolytic graphite (HOPG) at low halogen concentrations (1:<2 Co:I ratios) presented random individual Co(OEP)I molecules weakly adsorbed onto a hexagonal (HEX) CoOEP monolayer. Images of 1:2 Co:I ratio solutions, showed phase segregated HEX CoOEP and pseudo-rectangular (REC) Co(OEP)I incorporating one solvent molecule per Co(OEP)I. The REC structure formed in long parallel rows with the number of rows increasing with increasing solution I2. In this case, the presence of CoOEP on the surface was attributed to the spontaneous reduction of Co(OEP)I by the graphite substrate. DFT calculations indicate that the REC Co(OEP)I:PhO form is energetically more stable than the HEX form of Co(OEP)I on HOPG. Experimental STM images and DFT calculated adsorption energies and STM images support our interpretation of the observed structures.
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- PAR ID:
- 10589201
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The Journal of Physical Chemistry C
- Volume:
- 129
- Issue:
- 16
- ISSN:
- 1932-7447
- Page Range / eLocation ID:
- 7717 to 7729
- Subject(s) / Keyword(s):
- STM Surface reaction Density functional theory adsorption energy Solvent incorporation polymorphs
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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