Alkyne-based cyclooligomers: Synthesis, new architectures, and their supramolecular organizations

ORGN 658

Jeffrey S. Moore, jsmoore@uiuc.edu1, Ling Zang, lzang@chem.siu.edu2, C. Scott Hartley1, Erin L. Elliott1, Yunyi Lu, jsmoore@uiuc.edu1, and Chao Wang1. (1) Department of Chemistry, University of Illinois, Urbana, IL 61801, (2) Department of Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL 62901
Shape-persistent arylene ethynylene macrocycles have attracted great attention in the fields of supramolecular chemistry and materials science due to their unique structures, novel properties and potential applications. In this contribution, recent examples of macrocycle synthesis via either cross-coupling reactions or dynamic covalent chemistry (DCC) will be presented. Cyclooligomerization under kinetic control is impeded by the problem of product “overshooting”. Under reversible conditions, the product distribution is determined by thermodynamic stability; shape-persistent macrocycles encode enthalpy parameters into each monomer, while entropy favors the smallest possible cyclooligomer. Remaining synthetic challenges include new methods for the efficient preparation of site-specifically functionalized structures and larger, more complex two-dimensional and three-dimensional molecular objects. Self-assembly of shape-persistent macrocycles into nanofibrils will be demonstrated.

 

Modern Acetylene Chemistry
1:20 PM-4:55 PM, Wednesday, 13 September 2006 Moscone Center -- Room 134, Oral

Division of Organic Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006