Materials Chemistry Initiative

Our work was generously supported by the Materials Chemistry Initiative of the National Science Foundation, the Materials Science Center at Cornell University, the Office of Naval Research, the Army Research Office, Dow Chemical Co., and Xerox Corp. Special thanks to to Dr. James H. White and Mark Bommarito as well as to Dr. Michael J. Bedzyk (CHESS), Michael Albarelli, David Acevedo, Dr. Martin McMillan, and Dr. Ben Ocko (Brookhaven National Laboratories). 

As Director of the Division of Chemistry at the National Science Foundation, Hancock pioneered many new initiatives, especially those that encouraged interdisciplinary and international collaborations. He had an expansive view of chemistry as a science and urged chemists to pursue imaginative research on the discipline s traditional boundaries that would expand chemistry s frontiers. In materials chemistry, he saw a vital and growing area to which chemists could make important contributions. Under his leadership, the Division s support for research in materials chemistry grew to over 20 million in 1993. 

Materials chemistry proposals were jointly reviewed and split-funded, and in 1987 and 1988, 33 cooperative research projects were initiated. In 1989, the partnership was expanded to include the Division of Chemical and Thermal Systems (NSFs home for chemical engineering), and the program was renamed Materials Chemistry and Chemical Processing (MCCP). In 1989, 1990, and 1991, each of the three participating NSF divisions invested about three-quarters of a million dollars in additional... 

The total 5-year investment in the materials chemistry programs (MC and MCCP) was more than 18 million. That number might be considered modest, but MC-MCCP accomplished two things (1) it initiated about 60 collaborative research projects in the chemistry research community, where individualism was the overwhelming norm and (2) it established within NSF a paradigm for interdivisional cooperation in the review and funding of interdisciplinary research. 

Controlling the size, shape and ordering of synthetic organic materials at the macromolecular and supramolecular levels is an important objective in chemistry. Such control may be used to improve specific advanced material properties. Initial efforts to control dendrimer shapes involved the use of appropriately shaped core templates upon which to amplify dendritic shells to produce either dendrimer spheroids or cylinders (rods). The first examples of covalent dendrimer rods were reported by Tomalia et al. [43] and Schluter et al. [44], These examples involved the reiterative growth of dendritic shells around a preformed linear polymeric backbone or the polymerization of a dendronized monomer to produce cylinders possessing substantial aspect ratios (i.e. 15-100) as observed by TEM and AFM. These architectural copolymers consisting of linear random... 

Hiibner, G. and Roduner, E. 1999. EPR investigation of HO radical initiated degradation reactions of sulfonated aromatics as model compounds for fuel cell proton conducting membranes. Journal of Materials Chemistry 9 409- 18. 

The intensive development of the chemistry of homo- and heterometallic alkoxides of copper started more than 10 years ago in connection with the prospects of their application in the preparation of materials and initially in high temperature superconductors. In the search for the appropriate precursors in sol-gel and MOCVD techniques, attention was focused on the alkoxides of copper (I) and the fluorinated alkoxides of copper (II) — oligomeric derivatives soluble in non-polar solvents and existing not only in condensed but also in the gas phase. The derivatives of copper (II) and aliphatic alcohols, even rather branched or functional ones (such as alkoxyalkoxides) turned out to be polymeric substances uninteresting for further application. 

TTF (tetrathiafulvalene) and related compounds have been the subject of intense interest in the materials chemistry community because of their semi-conduction and superconduction properties. Recently, TTF has emerged as a unique radical initiator because its radical cation can be easily formed. The ease of formation is presumably derived from the favorable structure of the radical cation that incorporates an aromatic disulfonium salt and a very delocalized radical [49a]. Murphy et al. demonstrated a novel one-pot reaction cascade... 

A concerted focus on substitution would be an enormous boost to Green Chemistry initiatives by chemical producers and would allow creative new thinking to tackle the challenge of transitioning to more sustainable materials. 

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