Erasable Coordination Polymer Multilayers on Gold

Abstract

Metal–ligand interactions can be used to create coordination polymer multilayers (see picture). Growth is linear with layer and bilayer number, and the bilayer thickness depends on deposition concentration. This approach combines the stability of covalent multilayers with the responsiveness of polyelectrolyte‐based multilayers.

Synergism in Multicomponent Self-Propagating Molecular Assemblies

“…Excessive surface−solution exchange of the two molecular components would not have resulted in the multicomponent SPMAs. The Pd−pyridine coordination does not only create an excellent structural directing unit, − ,,− ,− ,, but it also is apparently stable enough to allow the incorporation of two different molecular building blocks having nearly identical binding motifs. This coordination chemistry has been studied extensively in solution to generate series of supramolecular structures with defined geometries and shapes, − some of which show interesting properties related to host−guest chemistry, sensing, storage, and catalysis.…”

Patterned Polymeric Multilayered Assemblies through Hydrogen Bonding and Metal Coordination

“…We also followed the hydrogen bonding multilayer formation using IR and UV–vis spectroscopies (Supporting Information). As described previously for our metal coordination multilayers, , we were able to show the stepwise increase in bilayer formation using UV–vis spectroscopy. While the combination of IR and UV–vis spectroscopies as well as our pattern-formation/AFM studies cannot prove the formation of multilayers through hydrogen bonding, the total absence of any multilayer formation without the deposition of 3 and the complete removal of patterns via a simple DMF rinse that is know to disrupt hydrogen bonds strongly suggests that the polymer multilayers are formed via hydrogen bonding.…”

“…Next, we investigated whether we can combine hydrogen bonding with metal coordination on a single patterned surface to create a dually responsive system. Previously, we have shown that the Pd–bispincer/PVP interaction can be used to assemble multilayered structures of controllable thicknesses. , Because of the solubility of the Pd–bispincer complex in DMF, which weakens significantly the hydrogen-bonding interaction between thymine and diaminopyridine, we carried out the metal coordination first in DMF followed by hydrogen bonding under the conditions described above.…”

“…The supramolecular interactions used in this contribution are metal coordination between a palladium–pincer complex and pyridine and the hydrogen bonding between thymine (THY) and diamidopyridine (DAP) (Figure ). It has been shown that the coordination between Pd–pincer complexes and pyridine is higher than 10 9 M –1 in chloroform while the association constant between thymine and DAP is on the order of 10 3 M –1 in halogenated solvents. , Previous work by our group has shown that the metal coordination between Pd–pincer complexes and poly(vinylpyridine) (PVP) can be used readily for the assembly of responsive and robust multilayers. − Furthermore, others have demonstrated that multilayered structures can also be assembled using other metal–ligand systems. − We have also employed the metal coordination between Pt–pincer complexes and pyridine to form supramolecular polymers. − Finally, we have demonstrated in solution that Pd–pincer-based metal coordination and the hydrogen bonding between THY and DAP are orthogonal to each other . We rationalize that the orthogonality of these two noncovalent interactions should hold true on surfaces providing us with a powerful tool by which external compounds can be introduced reliably to site-specific locations on surfaces.…”

Site-selective metal-coordination-based patterning of silane monolayers

“…23,24 We have introduced a surface functionalization strategy that uses coordination chemistry between pyridine and palladated pincer complexes thereby (i) providing for uniform film deposition, (ii) having a high degree of control of multilayer thickness, (iii) integrating a diverse set of polymer components, and (iv) affording stable, yet responsive multilayers that can be manipulated by chemical means. 25,26 In this study, we demonstrate a versatile methodology based on our metal-coordination surface functionalization strategy that integrates SAM photolithography (top-down) and molecular recognition directed self-assembly (bottom-up) strategies to create simple and rapidly synthesizable functional patterned surfaces.…”