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A macrocycle is, as defined by IUPAC, "a cyclic macromolecule or a macromolecular cyclic portion of a molecule."^[1] In the chemical literature, macrocycles varyingly include molecules containing rings of 8 or more atoms,^[1]^[2] or 12 or more atoms.^[2]^{[page needed]} In general, coordination chemists define a macrocycle more narrowly as a cyclic molecule with three or more potential donor atoms that can coordinate to a metal center. A well-known example is the group of drugs known as macrolides. The IUPAC definition notes that a "cyclic macromolecule has no end-groups but may nevertheless be regarded as a chain," and that "macrocycle is sometimes used [in the literature] for molecules of low relative molecular mass that are not considered 'macromolecules.^[3]

Macrocycle effect

Crystal structure of a Zn(II) ion coordinated to cyclen and ethanol reported in Inorg. Chem., 1997, 4579-4584.

The macrocyclic effect was discovered in 1969.^[3]^{[non-primary source needed]} Coordination chemists study macrocycles with three or more potential donor atoms in rings of greater than nine atoms, as these compounds often have strong and specific binding with metals.^[4]^{[page needed]} This property of coordinating macrocyclic molecules is termed the macrocycle effect, and is a special example of the chelate effect.^{[citation needed]}

Synthesis

In general, macrocycles are synthesized from smaller, usually linear, molecules.

Historical uses

Macrocycles have been in use for several decades as synthetic dyes. Phthalocyanine is a porphyrin analogue, which is arguably the most useful, in uses as dyes and pigments since their discovery in 1928, due to their dark-blue colour. However, there are many other uses for them. Their name comes from their synthetic precursor, phthalodinitrile.^[5]^{[page needed]}

Biological macrocycles

Heme, the active site in the hemoglobin (the protein in blood that transports oxygen), is a porphyrin containing iron.
Chlorophyll, the green photosynthetic pigment found in plants, contains a chlorin ring.
Vitamin B12 contains a corrin ring.

Related molecular categories

Ligand: an atom, ion, or functional group that is bonded to one or more central atoms or ions.
Chelate: a multidentate ligand, containing more than one donor atom.
Cryptand: a macrocycle with multiple loops (e.g., bicyclic).
Rotaxane: macrocycle(s) stuck on a stick, generally freely
Catenane: interlocked molecular rings (like a chain).
Molecular knot: a molecule in the shape of a knot such as a trefoil knot.

References

^ Still, W. C.; Galynker, I. Tetrahedron 1981, 37, 3981-3996.
^ J. D. Dunitz. Perspectives in Structural Chemistry (Edited by J. D. Dunitz and J. A. Ibers), Vol. 2, pp. l-70; Wiley, New York (1968)
^ "Glossary of basic terms in polymer science (IUPAC Recommendations 1996)" (PDF). Pure and Applied Chemistry 68 (12): 2287–2311. 1996. doi:10.1351/pac199668122287.

^ Parker, S.P. (2002). McGraw-Hill Science & Technology Dictionary. McGraw-Hill. ISBN 978-0070423138. ^{[page needed]}
^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version: (2006–) "macrocycle".
^ Milgrom, L.R (1997). The Colours of Life: An Introduction to the Chemistry of Porphyrins and Related Compounds. New York: Oxford University Press. ISBN 0-19-855380-3. (hardbound) ISBN 0-19-855962-3 (pbk.)^{[page needed]}
^ Cabbines, D. K.; Margerum, D. W. (1969). "Macrocyclic effect on stability of copper(II) tetramine complexes". J. Am. Chem. Soc. 91 (23): 6540–6541. doi:10.1021/ja01051a091. ^{[non-primary source needed]}
^ Melson, G.A., Ed. (1979). Coordination Chemistry of Macrocyclic Compounds. New York: Plenum Press. ISBN 0-306-40140-1. ^{[page needed]}
^ Jung, J.E.; Seung, S.Y. (2002). Bulletin of the Korean Chemical Society 23 (10): 1483–1486. doi:10.5012/bkcs.2002.23.10.1483. Missing or empty |title= (help)^{[better source needed]}^{[non-primary source needed]}

UpToDate Contents

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English Journal

Transition metal complexes of a new 15-membered [N5] penta-azamacrocyclic ligand with their spectral and anticancer studies.

El-Boraey HA1, Serag El-Din AA2.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.Spectrochim Acta A Mol Biomol Spectrosc.2014 Nov 11;132:663-71. doi: 10.1016/j.saa.2014.05.018. Epub 2014 May 20.
Novel penta-azamacrocyclic 15-membered [N5] ligand [L] i.e. 1,5,8,12-tetetraaza-3,4: 9,10-dibenzo-6-ethyl-7-methyl-1,12-(2,6-pyrido)cyclopentadecan-5,7 diene-2,11-dione and its transition metal complexes with Co(II), Ni(II), Cu(II), Ru(III) and Pd(II) have been synthesized and structurally character
PMID 24892547

Molecular modelling, spectroscopic characterization and biological studies of tetraazamacrocyclic metal complexes.

Rathi P1, Sharma K2, Singh DP2.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.Spectrochim Acta A Mol Biomol Spectrosc.2014 Sep 15;130:72-5. doi: 10.1016/j.saa.2014.03.046. Epub 2014 Apr 1.
Macrocyclic complexes of the type [MLX]X2; where L is (C30H28N4), a macrocyclic ligand, M=Cr(III) and Fe(III) and X=Cl-, CH3COO- or NO3-, have been synthesized by template condensation reaction of 1,8-diaminonaphthalene and acetylacetone in the presence of trivalent metal salts in a methanolic mediu
PMID 24769359

Cholinesterase sensor based on glassy carbon electrode modified with Ag nanoparticles decorated with macrocyclic ligands.

Evtugyn GA1, Shamagsumova RV2, Padnya PV3, Stoikov II3, Antipin IS3.
Talanta.Talanta.2014 Sep;127:9-17. doi: 10.1016/j.talanta.2014.03.048. Epub 2014 Apr 3.
New acetylcholinesterase (AChE) sensor based on Ag nanoparticles decorated with macrocyclic ligand has been developed and successfully used for highly sensitive detection of organophosphate and carbamate pesticides. AChE was immobilized by carbodiimide binding on carbon black (CB) layer deposited on
PMID 24913851

Japanese Journal

CHEMISTRY OF MACROCYCLIC β-LACTAM : AN OVERVEIW

Vangala Vijaya Bhaskar,Maddani Mahagundappa Rachappa,Hindupur Rama Mohan [他]
Heterocycles : an international journal for reviews and communications in heterocyclic chemistry 91(4), 701-717, 2015-04-01
NAID 40020423179

SYNTHESIS OF MACROCYCLIC PENTA- AND TETRAOXAZOLES AS G-QUADRUPLEX LIGANDS (Dedicated to Professor Isao Kuwajima on the occasion of his 77th birthday)

Masoud Shadi Sedghi,Tsushima Yamato,Iida Keisuke [他]
Heterocycles : an international journal for reviews and communications in heterocyclic chemistry 90(2), 866-873, 2015-01-01
NAID 40020329965