Design and synthesis of functional molecular architecture

The central theme of the research conducted by the Diederich group is the c reation of functional molecular architecture by design and advanced synthes is. Function is explored through interdisciplinary study, wherein national and international collaborations provide fertile grounds. Four areas of res earch are pursued: (i) In covalent fullerene chemistry, regio- and stereose lective templated synthesis protocols are developed to prepare three-dimens ional building blocks for supramolecular construction and advanced material s such as electrochemical ion sensors. (ii) Advanced materials are also tar geted by acetylenic scaffolding. Macrocyclic scaffolds of interest include perethynylated expanded radialenes featuring large Tc-conjugated all-carbon cores. Acyclic scaffolds such as monodisperse poly(triacetylene) (PTA) oli gomers, with linear, pi -conjugated all-carbon backbones expanding up to 18 nm length, are also actively investigated. Arylated tetraethynylethenes un dergo photochemical cis --> trans and trans --> cis isomerization without c ompeting thermal isomerization pathways - promising applications of these m aterials are foreseen in optical switching and memory storage devices. (iii ) In supramolecular chemistry, dynamic receptors are developed with the pot ential to function as,molecular grippers' on the single molecule level. Den dritic porphyrins are efficient models of hemoglobin and myoglobin and bind O-2 strongly and reversibly. They are also ideal model systems to explore the influence of the protein shell on the redox potential of the Fe-III/II couple in electron transfer proteins such as the cytochromes. (iv) Finally, the detailed understanding of molecular recognition principles generated i n the studies with artificial receptors provides the basis for a modern med icinal chemistry program aimed at the structure-based de novo design of non peptidic enzyme inhibitors.