Probing Metal Tip‐Induced Bond Weakening of a Reactive Alkyne Center Aligned via a Rigid Triphenylmethane‐Based Tripod on Au(111) by TERS and DFT

<jats:title>ABSTRACT</jats:title> <jats:p> The chemical reactivity of molecules can be controlled by a variety of effects, ranging from chemical reagents to purely physical stimuli. Metal tips employed in scanning probe microscopy are an elegant tool to manipulate reactive centers in single molecules. However, to achieve excellent control over distance and orientation, it is crucial to immobilize the reactive center and align it along the direction of the tip. Here, we aligned a reactive alkyne center via a rigid triphenylmethane‐based tripod for upright adsorption on Au(111) for inducing bond weakening in the alkyne moiety by approaching a silver tip. Single‐molecule ultrahigh vacuum low‐temperature tip‐enhanced Raman scattering was employed for probing tip‐induced bond weakening in the gap distance range from 550 to 250 pm. Both the ≡C–H stretching at ~3330 cm <jats:sup>−1</jats:sup> and the dominant –C≡C– stretching peak at ~2130 cm <jats:sup>−1</jats:sup> exhibit a shift to smaller wavenumbers due to tip‐induced bond weakening and an exponential increase in Raman intensity originating from the increased local electric field in the nanogap. To rationalize the underlying physical contributions and chemical effects of tip‐induced bond weakening, density functional theory calculations for gap distances in the range 800 to 100 pm were performed. The computational results confirmed the presence of different gap distance regimes including the onset of Pauli repulsion for short distances; for the latter, the calculations additionally predict structural distortions of the terminal alkyne induced by the nearby metal tip. These findings allow us to set a lower limit for the tip–tripod gap distance in studies requiring an intact upright configuration of the alkyne‐tripod, for example, electric field‐induced chemistry. </jats:p>