Heat transfer, electrical potential and light energy are common ways to activate chemical reactions. Applied force is another way, but dedicated studies for such a mechanical activation are limited, and this activation is poorly understood at the single-molecule level. Here, we report force-induced tautomerization in a single porphycene molecule on a Cu(110) surface at 5 K, which is studied by scanning probe microscopy and density functional theory calculations. Force spectroscopy quantifies the force needed to trigger tautomerization with submolecular spatial resolution. The calculations show how the reaction pathway and barrier of tautomerization are modified in the presence of a copper tip and reveal the atomistic origin of the process. Moreover, we demonstrate that a chemically inert tip whose apex is terminated by a xenon atom cannot induce the reaction because of a weak interaction with porphycene and a strong relaxation of xenon on the tip as contact to the molecule is formed
Here, we report the study of tautomerization within a single porphycene molecule adsorbed on a Cu(111) surface using low-temperature scanning tunneling microscopy (STM) at 5 K. While molecules are adsorbed on the surface exclusively in the thermodynamically stable trans tautomer after deposition, a voltage pulse from the STM can induce the unidirectional trans → cis and reversible cis ↔ cis tautomerization. From the voltage and current dependence of the tautomerization yield (rate), it is revealed that the process is induced by vibrational excitation via inelastic electron tunneling. However, the metastable cis molecules are thermally switched back to the trans tautomer by heating the surface up to 30 K. Furthermore, we have found that the unidirectional tautomerization can be remotely controlled at a distance from the STM tip. By analyzing the nonlocal process in dependence on various experimental parameters, a hot carrier-mediated mechanism is identified, in which hot electrons (holes) generated by the STM travel along the surface and induce the tautomerization through inelastic scattering with a molecule. The bias voltage and coverage dependent rate of the nonlocal tautomerization clearly show a significant contribution of the Cu(111) surface state to the hot carrier-induced process.
Electronic doping is a key concept for tuning the properties of organic materials. In bulk structures, the charge transfer between donor and acceptor is mainly given by the respective ionization potential and electron affinity. In contrast, monolayers of charge transfer complexes in contact with a metal are affected by an intriguing interplay of hybridization and screening at the metallic interface, determining the resulting charge state. Using scanning tunneling microscopy and spectroscopy, we characterize the electronic properties of the organic acceptor molecule 11,11,12,12-tetracyanonaptho-2,6-quinodimethane (TNAP) adsorbed on a Au(111) surface. The ordered islands remain in a weakly physisorbed state with no charge transfer interaction with the substrate. When the electron donor tetrathiafulvalene (TTF) is added, ordered arrays of alternating TNAP and TTF rows are assembled. In these structures, we find the lowest unoccupied molecular orbital (LUMO) of the free TNAP molecule shifted well below the Fermi level of the substrate. The TNAP is thus charged with more than one electron.
Tautomerization in single porphycene molecules is investigated on Cu(111), Ag(111), and Au(111) surfaces by a combination of low-temperature scanning tunneling microscopy (STM) experiments and density functional theory (DFT) calculations. It is revealed that the trans configuration is the thermodynamically stable form of porphycene on Cu(111) and Ag(111), whereas the cis configuration occurs as a meta-stable form. The trans → cis or cis → trans conversion on Cu(111) can be induced in an unidirectional fashion by injecting tunneling electrons from the STM tip or heating the surface, respectively. We find that the cis ↔ cis tautomerization on Cu(111) occurs spontaneously via tunneling, verified by the negligible temperature dependence of the tautomerization rate below ∼23 K. Van der Waals corrected DFT calculations are used to characterize the adsorption structures of porphycene and to map the potential energy surface of the tautomerization on Cu(111). The calculated barriers are too high to be thermally overcome at cryogenic temperatures used in the experiment and zero-point energy corrections do not change this picture, leaving tunneling as the most likely mechanism. On Ag(111), the reversible trans ↔ cis conversion occurs spontaneously at 5 K and the cis ↔ cis tautomerization rate is much higher than on Cu(111), indicating a significantly smaller tautomerization barrier on Ag(111) due to the weaker interaction between porphycene and the surface compared to Cu(111). Additionally, the STM experiments and DFT calculations reveal that tautomerization on Cu(111) and Ag(111) occurs with migration of porphycene along the surface; thus, the translational motion couples with the tautomerization coordinate. On the other hand, the trans and cis configurations are not discernible in the STM image and no tautomerization is observed for porphycene on Au(111). The weak interaction of porphycene with Au(111) is closest to the gas-phase limit and therefore the absence of trans and cis configurations in the STM images is explained either by the rapid tautomerization rate or the similar character of the molecular frontier orbitals of the trans and cis configurations.
Single-ion lanthanide-organic complexes can provide stable magnetic moments with well-defined orientation for spintronic applications on the atomic level. Here, we show by a combined experimental approach of scanning tunneling microscopy and X-ray absorption spectroscopy that dysprosium--tris(1,1,1-trifluoro-4-(2-thienyl)-2,4butanedionate) (Dy(tta)3) complexes deposited on a Au(111) surface undergo a molecular distortion, resulting in distinct crystal field symmetry imposed on the Dy ion. This leads to an easy-axis magnetization direction in the ligand plane. Furthermore, we show that tunneling electrons hardly couple to the spin excitations, which we ascribe to the shielded nature of the 4f electrons.
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