Morsali and Sayed Ali Akbar Razavi
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran, Iran
This edition first published 2021 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA and Scrivener Publishing LLC, 100 Cummings Center, Suite 541J, Beverly, MA 01915, USA
© 2021 Scrivener Publishing LLC
For more information about Scrivener publications please visit www.scrivenerpublishing.com.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or other- wise, except as permitted by law. Advice on how to obtain permission to reuse material from this title is available at http://www.wiley.com/go/permissions.
Wiley Global Headquarters
111 River Street, Hoboken, NJ 07030, USA
For details of our global editorial offices, customer services, and more information about Wiley prod- ucts visit us at www.wiley.com.
Limit of Liability/Disclaimer of Warranty
While the publisher and authors have used their best efforts in preparing this work, they make no representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials, or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read.
Library of Congress Cataloging-in-Publication Data
ISBN 9781119640431
Cover image: Pixabay.Com
Cover design by Russell Richardson
Set in size of 11pt and Minion Pro by Manila Typesetting Company, Makati, Philippines
Preface
As a subclass of coordination polymers and porous materials, metal– organic frameworks (MOFs) are composed of a dual organic–inorganic structure based on organic (organic linkers) and inorganic (metal ions/clusters) building blocks. In structural view, a unique kind of connection between organic linkers and inorganic nodes leads to construction of a three-dimensional framework with vacant spaces between building blocks. Owing to unlimited possibility in selection of organic ligands and metal ions/clusters, theoretically it is feasible to synthesis an unlimited number of frameworks.
In recent decades, MOFs received lots of attention in the world of material science and chemistry. Such tremendous attention is owing to their unique chemical characters such as hybrid organic–inorganic nature, high porosity and surface area, tunability in chemical functionality, highly ordered and crystalline structure and moderate-to-high chemical and thermal stabilities. Each one of these chemical properties enable MOFs to apply for specific purpose, but the ability to functionalize MOFs is a specific character to improve the capability of MOFs in different field of applications.
There are three ways for functionalization of MOFs including: (I) using functional organic linker, (II) pore functionalization through immobilization of other functional materials and (III) functionalization of inorganic nodes of the framework. Owing to versatile kind of organic functional groups, linker functionalization is recognized as a favorite strategy to tailor the chemical properties and enrich the host-guest chemistry of functional metal–organic frameworks (FMOFs).
In this book, we tried to review the literature to gain deep insight about the effects of linker functionalization on structure and host-guest chemistry of FMOFs. The content of this book is useful for gaining better understanding of the structural and chemical properties of FMOFs. Considering our strategy in this book, we believe that this book is interesting for diverse group of scientists like chemists, material engineers and anyone who is working on supramolecular chemistry of MOFs and designing functional materials.
The authors
October 2020
1
Introduction to Functional Metal–Organic Frameworks
Abstract
In this chapter, we discuss about the advantages of porous materials and crystalline materials and explain that what kinds of benefits are attainable if these advantages combine together in the structure of functional materials like metal-organic frameworks. Then, functional metal-organic frameworks are discussed and classified based on the roles of organic functions in the structure and application of MOFs.
Keywords: Porous materials, crystalline materials, functional metal-organic frameworks, coordination polymers, host-guest chemistry, function-application properties, function-structure properties
1.1 Coordination Polymers
Solid materials are generally classified in amorphous and crystalline (single-crystalline or poly-crystalline) solids in chemistry and material science. Crystalline solids are constructed based on periodic symmetrical arrays of constituents giving rise to definite, regular and repeating pattern of the solid in three dimensions over a large distance. Such long-range structural order rises in the beneficial fact that crystalline solids represent specific and repeatable chemical properties. This is a very pivotal advantage which is not observed in amorphous solids. For example, crystalline solids are of sharp melting point and definite heat of fusion while amorphous solids have not a characteristic heat of adsorption and sharp melting point. As a result, crystalline solids benefit from repeatable structure and chemical properties which are fitting characters in application of novel materials.
Another classification of materials is based on their porosity. Porosity, which also is called void fraction, is defined as the ratio of vacant space (void) in material to the total volume that the materials occupy. This fraction is always between 0 and 1. Porous materials encompass vacant spaces in their structure based on accessible pore volume (vacant cavities or channels) for guest molecules. This is a unique advantage of porous material in which not only can they interact with guest molecules on their surface, but also they can adsorb and interact with guests within their pores inside the bulk material. The characteristics of a porous material define by their surface area (m2·g−1), accessible pore volume (m3·g−1),