Tailored nano-spaces can control enantioselective adsorption and molecular motion. We report on the spontaneous assembly of adynamic system-a rigid kagome network with each pore occupied by ag uest molecule-employing solely 2,6-bis(1H-pyrazol-1-yl)pyridine-4-carboxylic acid on Ag(111). The network cavity snugly hosts the chemically modified guest, bestows enantiomorphic adsorption and allows selective rotational motions.T emperature-dependent scanning tunnelling microscopys tudies revealed distinct anchoring orientations of the guest unit switching with a0.95 eV thermal barrier.H -bonding between the guest and the host transiently stabilises the rotating guest, as the flapper on ar affle wheel. Density functional theory investigations unravel the detailed molecular pirouette of the guest and how the energy landscape is determined by H-bond formation and breakage.The origin of the guestse nantiodirected, dynamic anchoring lies in the specific interplay of the kagome network and the silver surface.

Ru-porphyrins act as convenient pedestals for the assembly of N-heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru-porphyrin monolayer, an extraordinary phenomenon can be observed: Ru-porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analysed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganisation can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalisation of surfaces with carbenes.

Tailored nano-spaces can control enantioselective adsorption and molecular motion. We report on the spontaneous assembly of adynamic system-a rigid kagome network with each pore occupied by ag uest molecule-employing solely 2,6-bis(1H-pyrazol-1-yl)pyridine-4-carboxylic acid on Ag(111). The network cavity snugly hosts the chemically modified guest, bestows enantiomorphic adsorption and allows selective rotational motions.T emperature-dependent scanning tunnelling microscopys tudies revealed distinct anchoring orientations of the guest unit switching with a0.95 eV thermal barrier.H -bonding between the guest and the host transiently stabilises the rotating guest, as the flapper on ar affle wheel. Density functional theory investigations unravel the detailed molecular pirouette of the guest and how the energy landscape is determined by H-bond formation and breakage.The origin of the guestse nantiodirected, dynamic anchoring lies in the specific interplay of the kagome network and the silver surface.

Ru‐porphyrins act as convenient pedestals for the assembly of N‐heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru‐porphyrin monolayer, an extraordinary phenomenon can be observed: Ru‐porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analysed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganisation can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalisation of surfaces with carbenes.

Aromatic foldamers are promising for applications such as molecular recognition and molecular machinery. For many of these, defect free, 2D-crystaline monolayers are needed. To this end, submonolayers were prepared in...