We present a combined scanning tunneling microscopy (STM), noncontact atomic force microscopy (nc-
AFM), and differential reflectance spectroscopy (DRS) study aiming at the characterization of the relationship between structural and optical properties of a supramolecular assembly of a curcuminoid derivative adsorbed on two kinds of substrates: bilayers of KCl on Au(111) [2 ML KCl/Au(111)] and KCl(001) bulk. The molecule features a difluoroboron (BF2) complex as well as cyano (CN) end groups, which induces an internal dipole moment of a few Debyes. The comparative study of the structural properties of the molecules adsorbed on 2 ML KCl/Au(111), which allows for STM characterization, and KCl bulk, which allows for nc-AFM and DRS characterization, shows that the molecular adsorption is similar on both substrates. STM and nc-AFM give evidence that the on-surface condensation of the molecules into supramolecular assemblies is steered by two main interactions: the molecule-substrate interaction between the CN end groups of the molecule and the cationic K+ species, as well as an in-plane intermolecular interaction involving BF2 and phenyl groups. Based on density functional theory calculations, we propose an epitaxial molecular structure described by a two-molecule unit cell forming an 8 × 2 supercell on the KCl surface that grows in form of ribbons along the or directions of the substrate, which are polar. Among several possible stereoisomers for the molecule, it is found that the balance between vertical and in-plane interactions selects the one whose size matches the distance
between K+ species to condense on the substrate and not the most stable one stemming from the gas phase.
Finally, optical spectroscopy in solvent and DRS measurements performed on the supramolecular assembly exhibit similar features identified as three absorption peaks tracing a π → π∗ electronic transition followed by a vibronic progression, plus a broader band featuring a set of higher-energy transitions. Due to both the weak electrostatic interactions and a lack of π-π interactions in the condensed molecular phase, DR spectra exhibit no major excitonic effect, but a nonrigid redshift of the molecular absorption band compared to the situation in solvent. This observation is found to be consistent with the isomer selection due to the transition from the gas phase to the on-surface condensed phase.
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DOI : 10.1103/PhysRevB.104.205415
Authors : Thomas Leoni, Laurent Nony, Elena Zaborova, Sylvain Clair, Frédéric Fagès, Franck Para, Alain Ranguis, Conrad Becker, and Christian Loppacher
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