History

The existence of intermolecular forces was first postulated by Johannes Diderik van der Waals in 1873. However, it is with Nobel laureate Hermann Emil Fischer that supramolecular chemistry has its philosophical roots. In 1890, Fischer suggested that enzyme-substrate interactions take the form of a "lock and key", pre-empting the concepts of molecular recognition and host-guest chemistry. In the early twentieth century noncovalent bonds were understood in gradually more detail, with the hydrogen bond being described by Latimer and Rodebush in 1920.

   The use of these principles led to an increasing understanding of protein structure and other biological processes. For instance, the important breakthrough that allowed the elucidation of the double helical structure of DNA occurred when it was realized that there are two separate strands of nucleotides connected through hydrogen bonds. The use of noncovalent bonds is essential to replication because they allow the strands to be separated and used to template new double stranded DNA. Concomitantly, chemists began to recognize and study synthetic structures based on noncovalent interactions, such as micelles and microemulsions.

   Eventually, chemists were able to take these concepts and apply them to synthetic systems. The breakthrough came in the 1960s with the synthesis of the crown ethers by Charles J. Pedersen. Following this work, other researchers such as Donald J. Cram, Jean-Marie Lehn and Fritz Vogtle became active in synthesizing shape- and ion-selective receptors, and throughout the 1980s research in the area gathered a rapid pace with concepts such as mechanically-interlocked molecular architectures emerging.

  The importance of supramolecular chemistry was established by the 1987 Nobel Prize for Chemistry which was awarded to Donald J. Cram, Jean-Marie Lehn, and Charles J. Pedersen in recognition of their work in this area.[4] The development of selective "host-guest" complexes in particular, in which a host molecule recognizes and selectively binds a certain guest, was cited as an important contribution.

  In the 1990s, supramolecular chemistry became even more sophisticated, with researchers such as James Fraser Stoddart developing molecular machinery and highly complex self-assembled structures, and Itamar Willner developing sensors and methods of electronic and biological interfacing. During this period, electrochemical and photochemical motifs became integrated into supramolecular systems in order to increase functionality, research into synthetic self-replicating system began, and work on molecular information processing devices began. The emerging science of nanotechnology also had a strong influence on the subject, with building blocks such as fullerenes, nanoparticles, and dendrimers becoming involved in synthetic systems.

Timeline of supramolecular chemistry

1810 – Sir Humphry Davy: discovery of chlorine hydrate
1823 – Michael Faraday: formula of chlorine hydrate
1841 – C. Schafhäutl: study of graphite intercalates
1849 – F. Wöhler: β-quinol H2S clathrate
1891 – Villiers and Hebd: cyclodextrin inclusion compounds
1893 – Alfred Werner: coordination chemistry
1894 – Emil Fischer: lock and key concept
1906 – Paul Ehrlich: introduction of the concept of a receptor
1937 – K. L. Wolf: the term Übermoleküle is coined to describe organised entities arising from the association
of coordinatively saturated species (e.g. the acetic acid dimer)
1939 – Linus Pauling: hydrogen bonds are included in the groundbreaking book The Nature of the Chemical Bond
1940 – M. F. Bengen: urea channel inclusion compounds
1945 – H. M. Powell: X-ray crystal structures of β-quinol inclusion compounds; the term ‘clathrate’ is
introduced to describe compounds where one component is enclosed within the framework of another
1949 – Brown and Farthing: synthesis of [2.2]paracyclophane
1953 – Watson and Crick: structure of DNA
1956 – Dorothy Crowfoot Hodgkin: X-ray crystal structure of vitamin B12
1959 – Donald Cram: attempted synthesis of cyclophane charge transfer complexes with (NC)2C
C(CN)2
1961 – N.F. Curtis: fi rst Schiff’s base macrocycle from acetone and ethylene diamine
1964 – Busch and Jäger: Schiff’s base macrocycles
1967 – Charles Pedersen: crown ethers
1968 – Park and Simmons: Katapinand anion hosts
1969 – Jean-Marie Lehn: synthesis of the fi rst cryptands
1969 – Jerry Atwood: liquid clathrates from alkyl aluminium salts
1969 – Ron Breslow: catalysis by cyclodextrins
1973 – Donald Cram: spherand hosts produced to test the importance of preorganisation
1978 – Jean-Marie Lehn: introduction of the term ‘supramolecular chemistry’, defi ned as the ‘chemistry of
molecular assemblies and of the intermolecular bond’
1979 – Gokel and Okahara: development of the lariat ethers as a subclass of host
1981 – Vögtle and Weber: podand hosts and development of nomenclature
1986 – A. P. de Silva: Fluorescent sensing of alkali metal ions by crown ether derivatives
1987 – Award of the Nobel prize for Chemistry to Donald J. Cram, Jean-Marie Lehn and Charles J. Pedersen for
their work in supramolecular chemistry
1996 – Atwood, Davies, MacNicol & Vögtle: publication of Comprehensive Supramolecular Chemistry
containing contributions from many key groups and summarising the development and state of the art
1996 – Award of the Nobel prize for Chemistry to Kroto, Smalley and Curl for their work on the chemistry of
the fullerenes
2003 – Award of the Nobel prize for Chemistry to Peter Agre and Roderick MacKinnon for their discovery of
water channels and the characterisation of cation and anion channels, respectively.
2004 – J. Fraser Stoddart: the fi rst discrete Borromean-linked molecule, a landmark in topological synthesis.

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