Molecularly doped metals.

The many millions of organic, inorganic, and bioorganic molecules represent a very rich library of chemical, biological, and physical properties that do not show up among the approximately 100 metals. The ability to imbue metals with any of these molecular properties would open up tremendous potential for the development of new materials. In addition to their traditional features and their traditional applications, metals would have new traits, which would merge their classical virtues such as conductivity and catalytic activity with the diverse properties of these molecules. In this Account, we describe a new materials methodology, which enables, for the first time, the incorporation and entrapment of small organic molecules, polymers, and biomolecules within metals. These new materials are denoted dopant@metal. The creation of dopant@metal yields new properties that are more than or different from the sum of the individual properties of the two components. So far we have developed methods for the doping of silver, copper, gold, iron, palladium, platinum, and some of their alloys, as well as Hg-Ag amalgams. We have successfully altered classical metal properties (such as conductivity), induced unorthodox properties (such as rendering a metal acidic or basic), used metals as heterogeneous matrices for homogeneous catalysts, and formed new metallic catalysts such as metals doped with organometallic complexes. In addition, we have created materials that straddle the border between polymers and metals, we have entrapped enzymes to form bioactive metals, we have induced chirality within metals, we have made corrosion-resistant iron, we formed efficient biocidal materials, and we demonstrated a new concept for batteries. We have developed a variety of methods for synthesizing dopant@metals including aqueous homogeneous and heterogeneous reductions of the metal cations, reductions in DMF, electrochemical entrapments, thermal decompositions of zerovalent metal carbonyls, and dissolution during amalgam formation. The structures of these dopant@metal materials indicate that metals entrap the organic molecules within their agglomerated nanocrystals. As a result, these materials are porous, making the dopant accessible for chemical reactions, in particular for catalysis. We have prepared these materials in a variety of forms, including powder, granules, pressed discs, thin films, thick films, sub-micrometer particles, and nanometric particles decorating ceramic nanofibers. Entrapment and adsorption are very different processes. If entrapped, water-soluble molecules cannot be extracted, but the same molecules, if adsorbed, are easily washed away. Likewise, most of the special properties that we have observed, such as major improvements or changes in catalytic activity, completely different thermal gravimetric analysis behavior, and more, are observed only in the entrapped cases.