Dynamic Metal-Phenolic Coordination Complexes for Versatile Surface Nanopatterning

We report a general nanopatterning strategy that takes advantage of the dynamic coordination bonds between polyphenols and metal ions (e.g., Fe3+ and Cu2+) to create structures on surfaces with a range of properties. With this methodology, under acidic conditions, 29 metal-phenolic complex-based precursors composed of different polyphenols and metal ions are patterned using scanning probe and large-area cantilever free nanolithography techniques, resulting in a library of deposited metal-phenolic nanopatterns. Significantly, post-treat-ment of the patterns under basic conditions (i.e., ammonia vapor) triggers a change in coordination state and results in the in situ generation of more stable networks firmly attached to the underlying substrates. The methodology provides control over feature size, shape, and composition, almost regardless of substrate (e.g., Si, Au, and silicon nitride). Under reducing conditions (i.e., H2) at elevated temperatures (180-600 degrees C), the patterned features have been used as nanoreactors to synthesize individual metal nanoparticles. At room temperature, the ammonia-treated features can reduce Ag+ to form metal nanostructures and be modified with peptides, proteins, and thiolated DNA via Michael addition and/or Schiff base reaction. The generality of this technique should make it useful for a wide variety of researchers interested in modifying surfaces for catalytic, chemical and biological sensing, and template-directed assembly purposes.

Automated summary

We developed a nanopatterning strategy based on the dynamic coordination bonds between polyphenols and metal ions, allowing the creation of structures on surfaces with diverse properties. By patterning metal-phenolic precursors composed of different polyphenols and metal ions under acidic conditions, a library of deposited metal-phenolic nanopatterns was obtained. Post-treatment of the patterns under basic conditions triggered a change in coordination state and led to the generation of stable networks attached to the substrates. This technique offers control over feature size, shape, and composition, making it useful for various applications such as catalysis, sensing, and template-directed assembly.