The combination of electrospray ionization with ion beam deposition in ultra-high vacuum has opened new opportunities to research non-sublimable molecules on solid surfaces in recent years. An Fe(II) [2 × 2] grid complex was deposited on Ag(111) and investigated by scanning tunneling microscopy. Low landing energies (< 3 eV z-1) resulted in clusters and single structures with potentially intact coordination bonds. Higher landing energies (> 3 eV z-1) led to coordination bond cleavage and a rich variety of self-assembled surface networks formed spontaneously by the grid fragments. Applying established on-surface synthesis methodology employing the constituents of these networks (ligands and Fe atoms) reproduced only a part of them. It is thus proposed that electrospray ion beam deposition is a different route to on-surface coordination network synthesis.

Preserving the structural integrity of biomimetic foldamers upon surface deposition is essential for their integration into functional molecular architectures and devices. When assembled in well-ordered monolayers, these molecules can exhibit distinctive characteristics. In this study, we investigate the electrospray-controlled ion beam deposition of foldamer molecules in an ultrahigh vacuum (UHV) environment on an Au(111) surface and examine how their conformation depends on the mean landing energy during deposition. At a low mean landing energy of about 0.6 eV, intact foldamers are observed on the surface, whereas higher landing energies predominantly result in unfolded molecules and partially folded states. Additionally, annealing of the substrate converts folded conformations into unfolded ones. These results highlight the importance of soft-landing conditions to maintain hydrogen-bond-stabilized architectures on surfaces, offering a model platform for studying the structure–function relationship of surface-supported thermolabile biomolecules.Preserving the structural integrity of biomimetic foldamers upon surface deposition is essential for their integration into functional molecular architectures and devices. When assembled in well-ordered monolayers, these molecules can exhibit distinctive characteristics. In this study, we investigate the electrospray-controlled ion beam deposition of foldamer molecules in an ultrahigh vacuum (UHV) environment on an Au(111) surface and examine how their conformation depends on the mean landing energy during deposition. At a low mean landing energy of about 0.6 eV, intact foldamers are observed on the surface, whereas higher landing energies predominantly result in unfolded molecules and partially folded states. Additionally, annealing of the substrate converts folded conformations into unfolded ones. These results highlight the importance of soft-landing conditions to maintain hydrogen-bond-stabilized architectures on surfaces, offering a model platform for studying the structure–function relationship of surface-supported thermolabile biomolecules.

Fabrication of diverse and complex 2D molecular architectures using surface-confined supramolecular coordination chemistry has been continuously attracting considerable attention for years. Here, the on-surface synthesis of 2D coordination networks exhibiting both crystalline and vitreous phases employing the same constituents is reported. Robust and flexible bimolecular 2D coordination networks, structurally analogous to 2D bilayer silica films on Ru(0001) and graphene, are achieved by iron-directed self-assembly of indigo and 1,3,5-tris[4-(pyridin-4-yl)phenyl]benzene (ext-TPyB) or 1,3,5-tris(pyridyl)benzene (TPyB) linkers on Au(111). The crystalline phase features honeycombed nanopores, displaying long-range order with local defects that can be attributed to variations in coordination nodes and shape flexibility of the ext-TPyB (/ TPyB) ligand. The vitreous phase evolves upon annealing the honeycomb network to higher temperatures and exhibits reticulated polygons similar to Zachariasen's 2D random network theory. The size of the polygons follows a lognormal distribution, with the probability density function showing an almost linear behavior as characteristic of the structure of glass. The results enrich avenues toward the fabrication and understanding of novel nanostructured condensed matter systems, such as 2D crystalline and vitreous structures, as well as provide the unique possibility to understand structurally bulk glasses.