Macrocyclic and Supramolecular Chemistry

How Izatt-Christensen Award Winners Shaped the Field

Reed M. Izatt

• Publisher: Wiley
• Year: 2016
• Print ISBN:
  9781119053842
• eBook ISBN:
  9781119053866
• Edition: 1
• Topic: Physical Sciences
• Subtopic: Physical & Theoretical Chemistry

This book commemorates the 25th anniversary of the International Izatt-Christensen Award in Macrocyclic and Supramolecular Chemistry. The award, one of the most prestigious of small awards in chemistry, recognizes excellence in the developing field of macrocyclic and supramolecular chemistry

Macrocyclic and Supramolecular Chemistry: How Izatt-Christensen Award Winners Shaped the Field features chapters written by the award recipients who provide unique perspectives on the spectacular growth in these expanding and vibrant fields of chemistry over the past half century, and on the role of these awardees in shaping this growth. During this time there has been an upsurge of interest in the design, synthesis and characterization of increasingly more complex macrocyclic ligands and in the application of this knowledge to understanding molecular recognition processes in host-guest chemistry in ways that were scarcely envisioned decades earlier.

In October 2016, Professor Jean-Pierre Sauvage and Sir J. Fraser Stoddart (author for chapter 22 "Contractile and Extensile Molecular Systems: Towards Molecular Muscles" by Jean -Pierre Sauvage, Vincent Duplan, and Frédéric Niess and 20 "Serendipity" by Paul R. McGonigal and J. Fraser Stoddart respectively) were awarded the Nobel Prize in Chemistry alongside fellow Wiley author Bernard Feringa, for the design and synthesis of molecular machines. 

1
The Izatt–Christensen Award in Macrocyclic and Supramolecular Chemistry: A 25-Year History (1991–2016)

Reed M. Izatt,^1,2 Jerald S. Bradshaw,^1,2 Steven R. Izatt,¹ and Roger G. Harrison²

¹ IBC Advanced Technologies, Inc., American Fork, UT, USA

² Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT, USA

1.1 Introduction

The Izatt–Christensen Award (I–C Award) recognizes excellence in macrocyclic and supramolecular chemistry. It has been presented annually since 1991 by the International Symposium on Macrocyclic and Supramolecular Chemistry (ISMSC). A common theme to both of these fields is molecular recognition. The search for underlying principles governing molecular recognition or how molecules recognize each other began in earnest in the early 1960s. Working independently, several individuals who later became prominent in the emerging fields of macrocyclic chemistry and supramolecular chemistry, made important early contributions to molecular recognition. Four of these were Charles J. Pedersen (1904–1989), Daryle H. Busch, Jean-Marie Lehn, and Donald J. Cram (1919–2001). Prior to the 1960s, no concentrated effort had been made to investigate chemical selectivity involving macrocyclic compound interactions with metal ions or other guest molecules [1] .

Charles Pedersen while employed at du Pont serendipitously discovered the compound that later came to be known as dibenzo-18-crown-6 (DBl8C6). Pedersen isolated DBI8C6 in a 0.4% yield from a “brownish goo” while attempting to prepare a completely different compound[2]. The decision to expend the effort needed to isolate, purify, and characterize the compound that became known as DBl8C6 represents a true example of scientific creativity and luck. The story of Pedersen’s discovery, reported in 1967, his identification of the many new cyclic polyether macrocyclic compounds he synthesized, his characterization of their selective complexation with alkali metal ions, and his own account of the events surrounding the discovery make fascinating reading [2, 3].

Daryle Busch remembers that his first ideas of synthesizing macrocycles occurred while a graduate student with John Bailar at the University of Illinois in the early1950s. His account of these first ideas of forming macrocycles from bidentate amines involved in copper(II) chelation illustrates the workings of a creative mind. It was several years later in 1962, as a Professor of Inorganic Chemistry at Ohio State University, that he reported the first synthesis of a macrocycle using a metal template [1, 5] He received the I–C Award in 1994 and is the author of a chapter in this book [4], in which he gives a first-hand account of his work.

Jean-Marie Lehn reported the synthesis of macrobicyclic polyethers containing three polyether strands joined by two bridgehead nitrogen atoms [6] in 1969, shortly after Pedersen’s initial paper. Lehn later coined the term, “supramolecular chemistry,” to describe the broadening of the scope of host–guest chemistry which he and his research group had spearheaded [7]. To quote Professor Lehn, “Beyond molecular chemistry, supramolecular chemistry aims at constructing highly complex, functional chemical systems from components held together by intermolecular forces.” These components can be visualized as host–guest systems bonded by intermolecular forces, which are much weaker than covalent chemical bonds. The guest systems may include organic guests as well as metal ions. The number and variety of hosts synthesized has expanded far beyond macrocyclic compounds. Lehn has provided an account of his early work [7].

Donald Cram was a prominent organic chemist in the 1960s. John Sherman [8], one of his Ph.D. students, describes him as “definitely old school. Eccentric. Hard driven. Strong-willed. Spirited. Fearless.” Cram’s accomplishments included a major research program in organic chemistry, co-author of three major organic chemistry textbooks, and instructor at UCLA of several generations of organic chemistry students. His first acquaintance with macrocyclic chemistry was recorded by Roeland Nolte who remembers [9] that during a stay as a visiting scientist in Cram...

Table of contents

• Cover
• Title Page
• Table of Contents
• List of Contributors
• Preface
• Acknowledgements
• 1 The Izatt–Christensen Award in Macrocyclic and Supramolecular Chemistry
• 2 Supramolecular Chemistry with DNA
• 3 Anion, Cation and Ion-Pair Recognition by Macrocyclic and Interlocked Host Systems
• 4 Perspectives in Molecular Tectonics
• 5 Three Tales of Supramolecular Analytical Chemistry
• 6 Robust Host–Guest Chemistry of Cucurbit[n]uril
• 7 Molecular Recognition in Biomimetic Receptors
• 8 A Lifetime Walk in the Realm of Cyclam
• 9 Porosity in Metal–Organic Compounds
• 10 Cyclodextrin-based Supramolecular Systems
• 11 Making the Tiniest Machines
• 12 Clipping an Angel’s Wings
• 13 From Lanthanide Shift Reagents to Molecular Knots
• 14 Texaphyrins
• 15 Macrocyclic Coordination Chemistry of Resorcin[4]arenes and Pyrogallol[4]arenes
• 16 Dynamic Control of Recognition Processes in Host–Guest Systems and Polymer–Polymer Interactions
• 17 Cation Binders, Amphiphiles, and Membrane Active Transporters
• 18 Supramolecular Technology
• 19 Synthesis of Macrocyclic Complexes Using Metal Ion Templates
• 20 Serendipity
• 21 Evolution of ZnII–Macrocyclic Polyamines to Biological Probes and Supramolecular Assembly
• 22 Contractile and Extensile Molecular Systems
• Index
• End User License Agreement