INCLUSION PHENOMENA AND MOLECULAR RECOGNITION INCLUSION PHENOMENA AND MOLECULAR RECOGNITION Edited by Jerry L. Atwood University of Alabama Tuscaloosa, Alabama PLENUM PRESS • NEW YORK AND LONDON Library of Congress Cataloging-In-Publication Data International Symposium on Inclusion Phenomena and Molecular Recognition (6th, 1988 Orange Beach. Ala.) Inclusion phenomena and molecular recognition I edited by ~erry L. Atwood. p. cm. "Proceedings of the Fifth International Symposium on InclUSion Phenomena and Molecular Recognition. held September 18-23. 1988. in Orange Beach. Alabama"--T.p. verso. Includes bibliographical references and index. ISBN-13:97B-I-4612-7BB7-0 e-ISBN-13:97B-I-4613-0603-0 001: 10.loo7/97B-I-4613-0603-0 1. Clathrate compounds--Congresses. I. Atwood. J. L. II. Title. QD474.159 1988 541.2·242--dc20 90-36651 CIP Proceedings of the Fifth International Symposium on Inclusion Phenomena and Molecular Recognition, held September 18-23, 1988, in Orange Beach, Alabama © 1990 Plenum Press, New York Softcover reprint of the hardcover 1st edition 1990 A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE The Fifth International Symposium on Inclusion Phenomena and Molecular Recognition was held September 18-23, 1988 at Orange Beach, Alabama. This followed previous very successful symposia in Warsaw (1980), Parma (1982), Tokyo (1984), and Lancaster (1986). The overall tone of the event at Orange Beach was expressed elegantly by Fraser Stoddart at the close of his lecture: "At a meeting like this, I think we should be asking ourselves more openly where we have come from and where we are going to. I am certainly willing to put my head on the block. Chemistry, as I see it, is entering a golden age of opportunity and those of us here who respond to the multidisciplinary challenge of the subject will perhaps start the movement to reunite the chemical sciences for the fIrst time in more than a century. Given the recognition granted through Charles Pedersen, Donald Cram, and Jean-Marie Lehn to our field from Stockholm last year, there are many here who are surely poised - if they have not already done so - to capture the academic high ground and intellectual leadership of our subject. And what is more - it will be on the back of our fundamental science that many of the exciting technological advances of the twenty-first century will be forged." In order to capture the flavor and excitement of the symposium, herein we present reviews by thirty-eight of the invited lecturers. The program was shaped by the Program Committee: Jerry L. Atwood, Richard A. Bartsch, George W. Gokel, Fredric M. Menger, Yuki to Murakami, and Galen D. Stucky. The local arrangements were overseen by Jerry L. Atwood, Duane C. Hrncir, William E. Hunter, Gregory H. Robinson, and Robin D. Rogers. The accompanying persons program was set up by Tracey M. Atwood. Financial support was generously provided by: Amoco Chemical Company, the Alabama Department of Economic and Community Affairs, Allied Signal, American Maize-Products Company, Dow Chemical Company, Eastman Kodak Company, Enraf Nonius, Nalco Chemical Company, Nicolet Instruments Corporation, v the Office of Naval Research, Serpentix, Inc., Technicon Instruments Corporation, and The University of Alabama. General guidance for the symposium was in the hands of the International Organizing Committee: G. D. Andreetti, J. L. Atwood, R. Breslow, J. E. D. Davies, Yu. A. Dyadin, T. Iwamoto, J.-M. Lehn, J. Lipkowski, D. D. MacNicol, W. Saenger, J. Szejt1i, F. Vogde, and R. L. Wife. Special thanks go to my Assistant Editor for this volume, Dr. Simon G. Bott, who oversaw all phases of the production of the camera-ready copy. November, 1989 Jerry L. Atwood NOTE: Asterisks appear in the author listings of certain chapters to designate the author to whom correspondence should be addressed. vi CONTENTS New Shapes for Catalysis and Molecular Recognition 1 J. Rebek, Jr. "Artificial Oligonucleotides": Molecular Recognition by Base Pairing 17 J. L. Sessler and D. Magda Optimizing the Neutral Molecular Receptor Properties of Water Soluble Cyclophanes 27 Craig S. Wilcox, Marlon D. Cowart, lIVing Sucholeiki, Rudolf R. Bukownik, and Vincent Lynch Complexation and Molecular Recognition of Neutral and Anionic Substrates in the Solid and Solution States by Bisparaquat(I,4)cyclophane 41 Mark V. Reddington, Neil Spencer, and J. Fraser Stoddart The Hexagonal Lattice Approach to Molecular Receptors 49 Thomas W. Bell, Albert Firestone, Jia Liu, Richard Ludwig, and Scott D. Rothenberger Molecular Recognition by Macrocyclic Receptors 57 Andrew D. Hamilton Host-Guest Binding Mechanisms: Experimental Approaches 65 Hans-Jorg Schneider, Thomas Blatter, Rudiger Kramer, Surat Kumar, Ulrich Schneider, and Isolde Theis Designed DNA Interactions 75 Kent D. Stewart A Novel Application of the Host-Guest Paradigm: Design of Organic Optoelectronic Materials 81 David M. Walba, Noel A. Clark, Homaune A. Razavi, and Devendra S. Parmar vii Complexes of Neutral Molecules and Cyclophane Hosts 93 Fran~ois Diederich Catalytic Functions of Paracyclophanes Based on Molecular Recognition 107 Yukito Murakami Synthesis and Complexing Properties of Chiral Guanidinium Receptors Designed for Molecular Recognition of Anions 119 Antonio Echavarren, Amalia Galan, Jean-Marie Lehn, and Javier de Mendoza Molecular Design of Calixarene-Based Host Molecules 125 Seiji Shinkai Complexation of Ions and Neutral Molecules by Functionalized Calixarenes 135 Rocco Ungaro, Andrea Pochini, and Arturo Arduini Biomimetic Ion Transport: Pores and Channels in Vesicle Membranes 145 V. E. Carmichael, P. J. Dutton, T. M. Fyles, T. D. James, C. McKim, J. A. Swan, and M. Zojaji Thermooynamics of Micellization for the K+ and Ba2+ Complexes of a Lipophilic Cryptand 151 Lourdes E. Echegoyen, Steve R. Miller, George W. Gokel, and Luis Echegoyen Redox Active Crowns: Towards the Second Generation 161 Stephen R. Cooper Heavy Metal Chemistry of Mixed Donor Macrocyclic Ligands: Strategies for Obtaining Metal Ion Recognition 171 Leonard F. Lindoy Lanthanide Chelates as Luminescent Probes 185 John L. Toner Catalytic Reactions of Macrocyclic Nickel(II) Complexes 199 Cynthia J. Burrows Shape Selective Oxidation as a Mechanistic Probe 209 Kenneth S. Suslick and Bruce R. Cook viii Novel Chromogenic Ionophores for Determination of Sodium and Potassium in Biological Fluids: Synthesis and Applications 217 Donald J. Cram, Eddy Chapoteau, Bronislaw P. Czech, Carl R. Gebauer, Roger C. Helgeson, and Anand Kumar From Real Chymotrypsin to Artificial Chymotrypsin: Myron L. Bender's Legacy 227 Valerian T. D'Souza Molecular Recognition by Cyclodextrin Hosts: Approach to New Functions 237 Iwao Tabushi, Kazuo Yamamura, and Yasuhisa Kuroda Fluorescence and Circular Dichroism Studies on Molecular and Chiral Recognition by Cyclodextrins 243 Koji Kano The Interactions of Vesicle-Forming Surfactants with Cyclodextrins 251 Orlando Garcia, Pablo A. Quintela, Jodi M. Schuette, Rafael Vargas, Hae R. Y oon, and Angel E. Kaifer Biomedical Uses of Amorphous Water-Soluble Derivatives of Cyclodextrins 261 Josef Pitha Inclusion and Reaction Chemistry of Two Anthracene-Appended y-Cyclodextrins 269 Akihiko Veno, Fumio Moriwaki, Akiko Azuma, and Tetsuo Osa Computer Simulations of Host-Guest Complexes 277 A. K. Cheetham and B. K. Peterson Photochemistry of Organic Molecules Adsorbed on Faujasite Zeolites: Steric Effects on Product Distributions 289 Nicholas J. Turro High Resolution Solid State NMR Studies of the Effect of Temperature and Adsorbed Organic Molecules on Zeolite Lattice Structures 299 C. A. Fyfe, G. T. Kokotailo, H. Gies, and H. Strobl Motion of Organic Species Occluded or Sorbed within Zeolites 325 J. M. Newsam, B. G. Silbernagel, M. T. Melchior, T. O. Brun, and F. Trouw ix Inclusion of Organometallics in Zeolite Host Structures 339 Thomas Bein, Karin Moller, and Aticha Borvomwattananont Photochemistry in Zeolite Cavities 351 V. Ramamurthy Artificial Photosynthesis in Zeolite-Based Molecular Assemblies 365 Jonathan S. Krueger, Cuiwei Lai, Zhuyin Li, James E. Mayer, and Thomas E. Mallouk Silver Sodalites: Novel Optically Responsive Nanocomposites 379 Geoffrey A. Ozin, Andreas Stein, Galen D. Stucky, and John P. Godber Surface Enhanced Luminescence with Silver Exchanged Zeolites 395 James F. Tanguay and Steve L. Suib Size Quantized Semiconductors in Porous Hosts -Quantum Dots 401 Norman Herron and Ying Wang Index 409 x NEW SHAPES FOR CATALYSIS AND MOLECULAR RECOGNITION Julius Rebek, Jr. Department of Chemistry University of Pittsburgh Pittsburgh, PA 15260 (USA) Any discussion of molecular recognition should begin by acknowledging the debt that it owes to macrocyclic chemistry. These molecules have been the workhorses of bioorganic chemistry and have influenced literally and figuratively the shape of things in molecular recognition. Cyclodextrins, for example, have been useful for showing how small molecules can imitate the essential steps of enzyme catalyzed reactions using acyl transfers as a probe [1]. Crown ethers have been successful at revealing aspects of binding and transport of metal ions; at the molecular level, complexation of ammonium species has been used as a vehicle for several bioorganic processes [2]. Allosteric effects, especially that of cooperativity were first demonstrated with crown ether derivatives [3]. More recently, interest in cyclophane derivatives has grown. Their ease of synthesis and their ability to complex aromatic molecules in aqueous media can be used to sort out the intrinsics of hydrophobic and aromatic stacking interactions. Some of the rules for predicting complexation especially those involving optimal rigidity and collapsibility have emerged from examination of cyclophane-derived systems. Despite their popularity, macrocyclic structures present some disadvantages. While such a shape is ideal for complexation of spherical substrates such as metal ions, these structures are quite difficult to functionalize on their interiors. That is, functional groups attached to macrocyclic structures tend to diverge and be directed away from the substrates held inside. In contrast, natural receptors such as enzymes and antibodies feature functional groups which converge on the substrates held inside. This convergence of functional groups, providing acids, bases, as well as shapes and sizes is, we believe, the key to molecular recognition in biological systems. It is no mere accident that nature often selects a structure resembling a cleft for this purpose. Such a shape offers easy access of the substrate into and out of it and provides a means by which selectivity can be engineered into it. By altering the lining of the cleft it is possible to tailor it into an exquisite, complementary fit for the substrate (Scheme 1). Inclusion Phenomena and Molecular Recognition Edited by J. Atwood Plenum Press, New York, 1990