Article

Shape-Persistent Macrocycles: Structures and Synthetic Approaches from Arylene and Ethynylene Building Blocks

Department of Materials Science and Engineering, University of Illinois, Urbana-Champaign, Urbana, Illinois, United States
Angewandte Chemie International Edition (Impact Factor: 11.34). 07/2006; 45(27):4416-39. DOI: 10.1002/anie.200503988
Source: PubMed

ABSTRACT Shape-persistent arylene ethynylene macrocycles have attracted much attention in supramolecular chemistry and materials science because of their unique structures and novel properties. In this Review we describe recent examples of macrocycle synthesis by cross-coupling (Sonogashira: aryl acetylene macrocycle or Glaser: aryl diacetylene macrocycle) and dynamic covalent chemistry. The primary disadvantage of the coupling methods is the kinetically determined product distribution, since a significant portion of oligomers grow beyond the length of the cyclic targets ("overshooting"). Better results have been obtained recently by a dynamic covalent approach involving reversible metathesis reactions that afford macrocycles in one step. Mechanistic studies demonstrate that macrocycle formation is thermodynamically controlled by this route. Remaining synthetic challenges include the efficient preparation of site-specifically functionalized structures and larger, more complex two- and three-dimensional molecules.

0 Followers
 · 
86 Views
  • [Show abstract] [Hide abstract]
    ABSTRACT: The reaction of 2,6-pyridinediylbis(3-pyridinyl)methanone (abbreviated as L) with various silver(I) salts yielded a series of complexes, namely, [Ag2(L)2](ClO4)2 (1), {[Ag2(L)2](ClO4)2}∞ (2), {[Ag2(L)2](NO3)2}∞ (3), {[Ag2(L)2](C2F5CO2)2}∞ (4), {[Ag2(L)2](C3F7CO2)2}∞ (5), and {[Ag2(L)2](O2CC3F6CO2)·2H2O}∞ (6), which exhibit a common dinuclear metallacyclic [Ag2(L)2]2+ skeleton that involves linear-dicoordinate AgI and μ2-N,N-bridging L. Complex 2 is a polymorph of 1 obtained by the solvent-medium tuning effect, and it has an {[Ag2(L)2]2+}∞ infinite-chain structure. In complexes 3–6, the argentophilic interaction plays an important role in connecting the [Ag2(L)2]2+ units to form a similar {[Ag2(L)2]2+}∞ chain structure to that in 2, although the counteranions are markedly different. The copper(II) complex {[Cu2(CH3CO2)4(L)]·2H2O}∞ (7) exhibits a zigzag-chain structure composed of an alternating arrangement of L and the Cu2(CH3CO2)4 paddlewheel cluster. In the supramolecular architectures of 1–7, the counteranions engage in multiple noncovalent interactions, and the presence of unusual types such as O/F(anion)···π, O/F(anion)···C=O, and C=O···π are noted and discussed.
    European Journal of Inorganic Chemistry 10/2013; 2013(30):5265-5273. DOI:10.1002/ejic.201300696 · 2.97 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to bring together in a single volume the many important aspects of hydrogen bonding supramolecular chemistry and will be a valuable resource for graduates and researchers working in supramolecular and related sciences.
    Hydrogen Bonded Supramolecular Structures, Edited by Li, Zhan-Ting, Wu, Li-Zhu, 01/2015: chapter 6: pages 187-225; Springer Berlin Heidelberg., ISBN: 978-3-662-45756-6
  • [Show abstract] [Hide abstract]
    ABSTRACT: This report details the advances in synthetic strategies toward arylene-ethynylene macrocycles (AEMs). After a brief description of traditional methods, we summarize recent advances based on dynamic covalent chemistry (DCC) whereby a highly active and functional group tolerant alkyne metathesis catalyst yields scalable quantities of AEMs under thermodynamic controlled reaction conditions.
    Pure and Applied Chemistry 10/2012; 84(4). DOI:10.1351/PAC-CON-11-09-15 · 3.11 Impact Factor