Abstract
<jats:p>To establish a systematic strategy for the controlled immobilization of functional organicinorganic hybrids involving a hexavanadate core, a series of thiophene-functionalized V6 conjugates (V6–SX) are synthesized and fully characterized. Their adsorption behavior on Au(111) is investigated by combining scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). All compounds exhibit a general tendency to adsorb on Au(111). However, the resulting surface organization is found to depend strongly on the molecular structure of the organic-inorganic hybrids, adsorption conditions, and solvent. As a consequence, a wide range of nanoscale architectures is obtained, including single molecules, sparse aggregates, compact monolayers, multilayers, and larger molecular agglomerates. Scanning tunneling spectroscopy (STS) measurements reveals the characteristic four-step resistive switching behavior of V6-based molecules immobilized on the surface. Notably, the optimized V6/Au(111) interface exhibits exceptional stability of the immobilized molecules, enabling both forward and backward potential sweeps to be recorded within a single room-temperature STS experiment. These measurements provide the first direct experimental evidence of fully reversible, four-step switching of a V6–oxo core strongly coupled to a conductive metal surface.</jats:p>