Application of Physical Methods to Inorganic and Bioinorganic Chemistry

Edited by Robert A. Scott and Charles M. Lukehart

ISBN 978-0-470-03217-6

Nanomaterials: Inorganic and Bioinorganic Perspectives

Edited by Charles M. Lukehart and Robert A. Scott

ISBN 978-0-470-51644-7

Computational Inorganic and Bioinorganic Chemistry

Edited by Edward I. Solomon, R. Bruce King and Robert A. Scott

ISBN 978-0-470-69997-3

Radionuclides in the Environment

Edited by David A. Atwood

ISBN 978-0-470-71434-8

Energy Production and Storage: Inorganic Chemical Strategies for a Warming World

Edited by Robert H. Crabtree

ISBN 978-0-470-74986-9

The Rare Earth Elements: Fundamentals and Applications

Edited by David A. Atwood

ISBN 978-1-119-95097-4

Metals in Cells

Edited by Valeria Culotta and Robert A. Scott

ISBN 978-1-119-95323-4

Metal-Organic Framework Materials

Edited by Leonard R. MacGillivray and Charles M. Lukehart

ISBN 978-1-119-95289-3

Forthcoming

The Lightest Metals: Science and Technology from Lithium to Calcium

Edited by Timothy P. Hanusa

ISBN 978-1-11870328-1

Sustainable Inorganic Chemistry

Edited by David A. Atwood

ISBN 978-1-11870342-7

Encyclopedia of Inorganic and Bioinorganic Chemistry

The Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC) was created as an online reference in 2012 by merging the Encyclopedia of Inorganic Chemistry and the Handbook of Metalloproteins. The resulting combination proves to be the defining reference work in the field of inorganic and bioinorganic chemistry. The online edition is regularly updated and expanded. For information see:

www.wileyonlinelibrary.com/ref/eibc

International Advisory Board

Michael Bruce

Adelaide, Australia

Tristram Chivers

Calgary, Canada

Valeria Culotta

MD, USA

Mirek Cygler

Saskatchewan, Canada

Marcetta Darensbourg

TX, USA

Michel Ephritikhine

Gif-sur-Yvette, France

Robert Huber

Martinsried, Germany

Susumu Kitagawa

Kyoto, Japan

Leonard R. MacGillivray

IA, USA

Thomas Poulos

CA, USA

David Schubert

CO, USA

Edward I. Solomon

CA, USA

Katherine Thompson

Vancouver, Canada

T. Don Tilley

CA, USA

Karl E. Wieghardt

Mülheim an der Ruhr, Germany

Vivian Yam

Hong Kong

The success of the Encyclopedia of Inorganic Chemistry (EIC), pioneered by Bruce King, the founding Editor in Chief, led to the 2012 integration of articles from the Handbook of Metalloproteins to create the newly launched Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC). This has been accompanied by a significant expansion of our Editorial Advisory Board with international representation in all areas of inorganic chemistry. It was under Bruce's successor, Bob Crabtree, that it was recognized that not everyone would necessarily need access to the full extent of EIBC. All EIBC articles are online and are searchable, but we still recognized value in more concise thematic volumes targeted to a specific area of interest. This idea encouraged us to produce a series of EIC (now EIBC) Books, focusing on topics of current interest. These will continue to appear on an approximately annual basis and will feature the leading scholars in their fields, often being guest coedited by one of these leaders. Like the Encyclopedia, we hope that EIBC Books continue to provide both the starting research student and the confirmed research worker a critical distillation of the leading concepts and provide a structured entry into the fields covered.

The EIBC Books are referred to as spin-on books, recognizing that all the articles in these thematic volumes are destined to become part of the online content of EIBC, usually forming a new category of articles in the EIBC topical structure. We find that this provides multiple routes to find the latest summaries of current research.

I fully recognize that this latest transformation of EIBC is built on the efforts of my predecessors, Bruce King and Bob Crabtree, my fellow editors, as well as the Wiley personnel, and, most particularly, the numerous authors of EIBC articles. It is the dedication and commitment of all these people that are responsible for the creation and production of this series and the “parent” EIBC.

Robert A. Scott

University of Georgia

Department of Chemistry

October 2014

The field of metal-organic frameworks (MOFs) has experienced explosive growth in the past decade. The process of mixing readily available metal precursors with organic linkers has captured the imagination of chemists and materials scientists worldwide to an extent that discussions on uses of MOFs for energy storage, catalysis, and separations, as well as integrations into technologies such as fuel cells and electronics, have become commonplace. At the core of the explosion are uses of fundamental principles that define our understanding of inorganic chemistry and, more specifically, coordination chemistry. A main thesis that drives the design and formation of a MOF is that the linking of components will be sustained by coordination bonds and that the linkages will be propagated in space to reflect coordination geometries and requirements of metals. A critical backdrop is the field of solid-state chemistry that provides primary assessments and insights into the structure and properties of MOFs where concepts of crystal engineering help to drive new directions in design, synthesis, and improvement. Organic synthesis plays a vital role in not only the formation of molecules that link metals but also equipping a MOF with function that can be tailored. Moreover, it has been synergism between these highly fundamental disciplines that, collectively, have enabled the field of MOFs to grow and flourish to the exciting and highly interdisciplinary status that the field enjoys today.

Metal-Organic Framework Materials covers topics describing recent advances made by top researchers in MOFs including nanoparticles and nanoscale frameworks, mesoporous frameworks, photoreactive frameworks, polyrotaxane frameworks, and even edible frameworks, as well as functionalized frameworks based on porphyrins, fluorine, and aluminum. In addition, the volume features aspects on mechanochemical synthesis and post-synthetic modification, which provide discussions on new vistas on the “before” and “after” of framework design and construction.

Metal-Organic Framework Materials also gives up-to-date descriptions of the many properties and applications evolving from MOFs. Magnetic properties are highlighted as related to formates and single-molecule magnets while host–guest properties are discussed in terms of uptake and sequestering of gases, hydrocarbons, alcohols, and metals, as well as uses of open metal sites and photoreactive components in host design. Applications of MOFs to semiconductors, materials for patterning, integrations in mixed-matrix membranes, uses in electrochemical materials, and uses in analytical chemistry are also presented. Investigations that stem from solid-state chemistry based on characterizing MOFs using solid-state NMR analyses as well as studying single-crystal reactions of MOFs and understanding interpenetration and entanglement help us further understand the fundamentals of the field.

While the rapid and accelerating development of MOFs will prohibit a comprehensive treatment of the status of the field, we believe that Metal-Organic Framework Materials provides readers a timely update on established and fresh areas for investigation. The reader will develop firsthand accounts of opportunities related to fundamentals and applications of MOFs, as well as an emerging role of MOFs in defining a new materials space that stems from the general and main topic of inorganic chemistry.

Leonard R. MacGillivray

University of Iowa

Iowa City, IA, USA

Charles M. Lukehart

Vanderbilt University

Nashville, TN, USA

October 2014

PART 1
Design and Synthesis