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Chirality

F. Richard Keene
James Cook University, Townsville, Queensland, Australia

1 Introduction
2 Practical Aspects
3 Metallosupramolecular Chemistry
4 Helicates
5 Catenanes and Molecular Knots
6 Chiral Polyhedra
7 Conclusions
References
Further Reading

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The development of artificial supramolecular assemblies—where smaller component molecular species form
finite aggregates through noncovalent interactions—and the
factors involved in their formation have been addressed in
other contributions of this series. The additional feature of
supramolecular chirality arises when the assembly itself is
asymmetric or dissymmetric. This situation can arise in one
of four ways:
1.
2.

3.

1

INTRODUCTION

Chirality (or “handedness”) is the property of an object
being not superimposable on its mirror image form. Such
a phenomenon arises when the object does not possess a
plane, center, or inversion axis of symmetry—it may still
possess chirality if it has proper axes of symmetry, in which
case it is referred to as dissymmetric; if it has no symmetry,
it is referred to as asymmetric.
Despite a continuing debate about the origins of molecular chirality, its presence in living systems is ubiquitous.
The efficiency of biological processes serves as a continual challenge to chemists in terms of the design of artificial
systems that possess a similar capacity in terms of stereoselectivity and catalytic efficiency, and the aspect of chirality
remains a key feature for such artificial systems.

4.

the components of the assembly are chiral;
the components are achiral but the aggregate is asymmetric/dissymmetric, in which case a racemic mixture
of chiral forms results;
the creation of the structure involves a chiral component, and subsequent elaboration with achiral components preserves the memory of the initial chirality; and
a chiral capsule aggregate is formed around a chiral
guest.

The phenomenon in (4) is to be distinguished from chiral
recognition, which relates to the interaction of a chiral
guest with an existing chiral cavity in a supramolecular
aggregate. Clearly, this alternative aspect has significant
relevance in the design of supramolecular assemblies as
there are implications for the recognition of chiral targets.
The creation of chiral cavities in supramolecular aggregates
may profoundly influence chiral catalytic processes that
take place within them, which has significance because
such processes have a fundamental importance in synthetic
chemistry.
The nature of the “noncovalent” interactions between
molecular components, which give rise to supramolecular
assembly, can include hydrogen bonding (which is common in natural systems), π –π stacking, ion/dipole interactions, and dispersion forces. Somewhat controversially,
coordination bond (metal–ligand) associations may also be

Supramolecular Chemistry: From Molecules to Nanomaterials, Online  2012 John Wiley & Sons, Ltd.
This article is  2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc015

so that the conversion of a racemic mixture to a diastereoisomeric mixture using a chiral auxiliary (as in point 1) prior to chromatography may be efficacious. In inorganic chemistry where ions are involved. chromatography. Chiral shift reagents—usually chiral lanthanide complexes—are added to the mixture of enantiomers. bond angles. the properties of enantiomers will also be identical unless the environment is chiral. In the absence of such a reference probe. Online  2012 John Wiley & Sons. DOI: 10. the enantiomeric forms have different (mirror image) geometries and may be separated visually—the case of the separation of the two enantiomeric forms of sodium ammonium tartrate tetrahydrate crystals by Louis Pasteur being a classic example. resulting in two compounds that are diastereoisomers (≥2 chiral centers)—and since diastereoisomers have different physical properties. melting points. and these cases have been well surveyed in a recent book on “Supramolecular Chirality. For the case of the weak intermolecular noncovalent association that does not involve metal–ligand interaction. 2. 1. Given the necessity for a chiral environment to differentiate enantiomeric forms. the use of an enantiomerically pure counterion will give rise to diastereoisomeric salts that can allow differentiation of the chiral forms under conditions of strong ion association. However. and in cases where they associate differently with the two enantiomers. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. the use of a chiral counterion will give rise to diastereoisomeric salts that can be separated. boiling points.2 Identification and quantification of chirality The measurement of chirality may be achieved in one of three ways—X-ray diffraction. etc. Ltd. it leads to Supramolecular Chemistry: From Molecules to Nanomaterials. Ltd. In both cases. the individual enantiomers can be isolated from the separated diastereoisomers. For charged chiral ions. In other cases. 2. since the separation of diastereoisomers is not subject to the condition of the chiral environment.1 PRACTICAL ASPECTS Separation of enantiomers (“resolution”) As the vast majority of physical and chemical characteristics of chiral (enantiomeric) forms of a molecule are identical (bond lengths. 1. Chromatography can also be used to separate chiral forms of molecules. in which case a precursor is chiral and that configurational feature is conserved during the synthetic process. but in many cases can be achieved by an analysis that takes into account the phase of the diffused wave—this procedure is aided when there are heavier atoms present so that it works more satisfactorily for metal-containing species. enantiomers may be derivatized with a chiral substituent. NMR spectroscopy. and so on. separation may be achieved by fractional crystallization. 2. spectra. This article is  2012 John Wiley & Sons. Resolution of enantiomers can be divided into two categories. Accordingly. NMR is widely used in the determination of structure and enantiomeric excess. which requires that a racemic compound crystallizes in a chiral unit cell. more commonly. diastereoisomers can be chromatographically separated on an achiral support using an achiral eluent. resolution can only be achieved where the chromatographic medium is chiral and/or the eluent is chiral. there are a large number of examples.1 The present overview of chirality in supramolecular systems will concentrate on aggregates formed using metal–ligand interactions.). As an alternative general procedure. and chiro-optical methods. The chiral forms of molecules may in some cases be obtained by enantioselective synthesis. but it cannot distinguish between enantiomers per se. Ltd.smc015 .” to which the reader is referred. the enantiomers need to be converted to diastereoisomers—which may be differentiated and therefore the enantiomeric configuration derived. The separation of a mixture of chiral isomers (racemate) reflects this situation.2 Concepts included (giving the so called metallosupramolecular aggregates). resolution is achieved by the use of chiral auxiliaries: the two enantiomers of a racemic mixture form compounds with an auxiliary of one fixed chirality. and are aided by the presence of a chiral marker (such as provided by being in a diastereoisomeric salt). 2 2. Such a procedure may be achieved as a consequence of stereoselectivity. This can be achieved in a number of ways: (a) (b) In organic chemistry. stereospecificity may be utilized where a chiral feature in the precursor induces a stereochemical preference in the other regions of the product. the determination of the configuration of an enantiomer may prove difficult. There are two general ways in which chiral forms may be separated—resolution or chromatography—or they may be obtained by enantioselective synthesis.1002/9780470661345. The first is the relatively rare phenomenon of spontaneous resolution. Single crystal X-ray diffraction determinations may be used. When the resultant crystals are of reasonable size. or when a chiral catalyst is used. polarities.

” Linearly polarized light has two components that are circularly polarized (helical) in opposite directions. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. is a fundamental property of chiral molecules. A substance may give rise to a number of Cotton effects in its ORD. be asymmetric or dissymmetric so that they are nonsuperimposable on their mirror image). VCD). as α does depend on λ. Notwithstanding those vagaries. In cases where the particular compound absorbs. which is dependent on the concentration. There have been a substantial number of reviews and books which have probed aspects of the issue of stereochemistry in metallosupramolecular assemblies.10 Sauvage et al. thus modifying the polarization plane by an angle α. the [α] is often recorded as a function of λ—called the optical rotatory dispersion (ORD).2 The seminal work of Caulder and Raymond3 and Stang et al. and rotaxanes. a Cotton effect will be observed in the region of an absorption.12 Significantly. different shifts in some NMR resonances for the two enantiomers. (a) For a chiral molecule. a plot of ε against λ gives rise to circular dichroism (CD). 120◦ . catenanes. the work of Dietrich-Buchecker and Sauvage8 utilizing metal centers as templates in the formation of intricate knots. The resultant inflection point is called a Cotton effect and can be negative or positive depending on its direction.7 to probe nonclassical molecular interactions are but some examples (among many) of this significant area of current research in coordination chemistry. while the development of molecular assemblies in organic chemistry was built on a prior understanding of the nature of the geometry of the carbon atom (tetrahedral/trigonal/linear). This discussion is intended to provide only a summary of the practical aspects of the separation and identification of enantiomers. the refractive index goes through a maximum and minimum with a point of inflection. the phenomenon of the self-assembly of very specific structures is possible.. 13. the specific rotation [α]T λ may be quoted at a single wavelength. 14 This Supramolecular Chemistry: From Molecules to Nanomaterials. where two enantiomeric forms of a molecule will rotate the plane of polarized light equally in opposite directions. or octahedral (90◦ or 180◦ )— geometric isomerism/diastereoisomerism can give rise to alternate forms. These two components will travel through a chiral medium at different speeds. Ltd. but the curves will be strictly equal and opposite for the two enantiomers.1. and the reader is referred to some of these to gain an appreciation of the rapid progress. 3 3 METALLOSUPRAMOLECULAR CHEMISTRY One of the significant features of metallosupramolecular chemistry is the potential for the assemblies to include a multitude of structural motifs..9 Balzani et al. and temperature. Online  2012 John Wiley & Sons. the present recent advances in metallosupramolecular chemistry have taken place not only with an additional complexity of the possible variations in component geometries but also with less established methodologies to control the stereochemistries of the component metal centers. DOI: 10.11 have shown the importance of the geometric versatility of the coordination environment in supramolecular design. and is the origin of the use of the rather strange term “optical isomers. to which the reader is referred (in Further Reading at the end of this chapter) for additional information. NMR studies in the presence of a chiral solvent or in chiral liquid crystals can give rise to diastereoisomeric associations. solvent. and as a consequence the ORD will show a point of inflection near that absorption. More detailed descriptions and variations are given in other excellent texts. arising from the variety of coordination geometries offered by the component metal centers. and in some cases the sign of the Cotton effect(s) in the CD may be used to identify absolute configuration of an enantiomer. Geometrical isomerism also arises in bis(bidentate) or tris(bidentate) centers where the bidentate ligands are unsymmetrical. crossing the x-axis. and the deliberate design of coordination cages by Fujita et al. The phenomenon of optical rotation. Ltd. However.Chirality (c) 3.e.1002/9780470661345. (b) As the absorption coefficients for the two circularly polarized components will be different when the electromagnetic radiation passes through a chiral medium. Coordinated metal centers may also provide the added nuance of stereoisomerism: the component center(s) may possess chirality (i. square planar (where two coordination positions can be disposed at 90◦ or 180◦ ). trigonal bipyramidal (90◦ . In cases where there is planned complementarity in a geometric and/or electronic sense. As for ORD. or in cases where the coordination geometry of a center involves more than one relative orientation of ligands—for example.smc015 . Ltd. which allow differentiation of the enantiomers. This article is  2012 John Wiley & Sons. or 180◦ ). and the development of the molecular machine concept by the research groups of Stoddart. an appreciation of the stereochemical issues has developed rapidly and there are many elegant examples of the growing mastery of the area. (c) CD may also be observed in the infrared region (vibrational circular dichroism.4–6 on high-symmetry architectures. In a similar way.

A number of these have involved the condensation of appropriate amines with the coordinated 1.2 Examples of stereoselective synthesis There are several examples of stereoretentive reactions that form oligonuclear species of predetermined stereochemistry.6-dione ligand in chiral precursor complexes of the type [Ru(pp)2 (phen-5. these examples are system specific and an alternative—and more generally applicable—strategy was sought in which an enantiomerically pure chiral building block would be used to produce mono. In a related system. Ltd. DOI: 10.smc015 . Within the class of mononuclear complexes containing bidentate ligands.21 The same research group used a similar method to obtain a D3 -symmetric tetranuclear species (Figure 5). and  diastereoisomers of the tpphz-bridged dimer (Figure 4).18 Lincoln and Nord´en19 have used this methodology to produce and -[{Ru(phen)2 }2 {dppz(11−11 )dppz}]4+ (Figure 2). MacDonnell and Bodige have used resolved precursors to form . in which the stereochemistries of the two ruthenium centers are predetermined ( and ) by the use of the same .2-diaminoethane (ethylenediamine) and its analogs. predominantly using cobalt complexes of 1.10-phenanthroline-5.or [Ru(phen)2 (1.20 Supramolecular Chemistry: From Molecules to Nanomaterials.22 However.10-phenanthroline-5.1.19 3. Ltd.15–17 While there have been many subsequent studies that have been concerned with the stereochemistry of mononuclear species of bidentate ligands. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. whereas for a bis(bidentate) complex involving two monodentate ligands there are geometric isomers (cis/trans) as well as enantiomers of the cis form.4 Concepts chapter is designed to emphasize some of the guiding principles of chirality in terms of the construction of such assemblies.20 have reported the complex shown in Figure 3. This article is  2012 John Wiley & Sons.and dinuclear 6+ N N N N (phen)2Ru Figure 3 N N N N N N N N Pt N N N N Ru(phen)2 Ru(phen)2 Stereoselective synthesis of diastereoisomers of a trimetallic species. N N (phen)2Ru N N N N N Figure 2 Stereoselective synthesis of diastereoisomers of [{Ru (phen)2 }2 {µ-dppz(11−11 )dppz}]4+ . Ltd. Online  2012 John Wiley & Sons. In such cases.1. . 2+ O N + 2 (phen)2Ru N 3.11 When the ligands are symmetrical (C2 symmetry). Sargeson and their coworkers.1002/9780470661345. resolved by diastereoisomer formation with the arsenyl-(+)-tartrate anion.10-phenanthroline). When the bidentate ligands are nonsymmetrical.1 NH2 H 2N O H 2N NH2 Building polymetallic assemblies with chiral components 3. the stereoisomeric possibilities increase exponentially with the number of metal centers. the samples obtained under normal synthetic conditions will be a mixture of stereoisomers in an uncertain ratio. the same basic principles are maintained.1 Stereochemistry in polymetallic assemblies 4+ N Stereoisomerism is possible in systems containing octahedral metal centers with bidentate ligands. In polynuclear species. and using a similar procedure. additional geometrical isomerism occurs.6-dione)]2+ precursor.6-dione)]2+ (pp = 2. chiral forms ( and  enantiomers) exist for the tris(bidentate) species (Figure 1). Lehn et al. the most detailed studies were originally undertaken by Dwyer. M M Λ ∆ Figure 1 Chiral (enantiomeric) forms of an octahedral tris (bidentate) metal complex.2 -bipyridine or 1.

2 -bipyridine (bpy) and 1. and their derivatives}.or -[Ru(bpy)2 (3-bromo-1.23. including chiral neutral species such as cis-[Ru(phen)2 X2 ] (X = CN− . derived from the reaction of the -[Ru(bpy)2 (3.1002/9780470661345. Tzalis and Tor31 reported the use of the bis(pyridine) precursor to produce chiral complexes of functionalized phen ligands.10-phenanthroline)]2+ with two moles of . Online  2012 John Wiley & Sons. The complexes [Ru(pp)2 (py)2 ]2+21 {pp are bidentate polypyridyl ligands such as 2. Cl− ) which are difficult to obtain by other means.O  -dibenzoyltartrate and antimonyl-tartrate anions. Ltd.2 -bibenzimidizole).10-phenanthroline (phen).10-phenanthroline)]2+ (Figure 7). Kane-Maguire and coworkers30 have reported the resolution of cis-[Ru(phen)2 (CH3 CN)2 ]2+ .smc015 . these researchers also reported the synthesis of the  and  diastereoisomers of the trinuclear species.8diethynyl-1. which may be used as a chiral precursor for further synthesis. 2+ O N (phen)2Ru Ru(phen)2 O 4+ N N N N N N (phen)2Ru Ru(phen)2 Figure 4 Stereoselective synthesis of diastereoisomers of [{Ru (phen2 }2 {µ-tpphz}]4+ .22 Supramolecular Chemistry: From Molecules to Nanomaterials. . or  stereochemistry (Figure 6).Chirality 2+ H2N N H2N N + N a decarbonylation procedure) with complete retention of stereochemical integrity under conditions where the length of the reaction and the temperature were controlled. 24 These chiral precursors were used to synthesize a wide range of mononuclear and ligand-bridged dinuclear and trinuclear species with predetermined stereochemistry. DOI: 10. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. Ltd. Yin and Eisenbaumer32 have reported the use of the same bis(pyridine) precursor to synthesize homochiral dinuclear and tetranuclear complexes of the bridging ligands 2. This article is  2012 John Wiley & Sons. In this work. Ltd. and [Ru(pp)(pp )(CO)2 ]2+ (pp = pp )22 —conveniently resolved by conventional diastereoisomer formation using the chiral forms of the O. which were subsequently linked to form dimers with predetermined .23–29 Additionally. respectively (Figure 8).2 bibenzimidizole and bis(2.21 species of predetermined stereochemistry. respectively—were found to undergo substitution of the two monodentate pyridine or carbonyl ligands (the latter in 8+ O O N N N 2+ N N O N N Λ Ru N N N O Ru N N O N N ∆ O N N ∆ 2+ H2N N N N N Ru N N N N N N N N N N N N N Ru N N Λ N ∆Λ3 N N Λ Λ Ru N N + 3 equivalents H2 N Ru N N Figure 5 5 Synthesis of a stereochemically controlled D3 -symmetric tetranuclear complex.

6 Concepts 2+ 2+ N N + (bpy)2Ru Ru(bpy)2 N N Br 4+ N N N Ru(bpy)2 N Ru(bpy)2 Figure 6 Stereoselective synthesis of diastereoisomers of alkyne-bridged dinuclear species. m.1.9. bpy. Keene et al. m = 0.42. In an imaginative approach.36–39 bpy {denoted CG[bpy]}. DOI: 10. b p m /b p m .31 2+ 2+ N N + 2 (bpy)2Ru Ru(bpy)2 N N Br 6+ N N Ru(bpy)2 N N Ru(bpy)2 N N By way of examples. b p m /b p m ) of the heteroleptic homometallic trinuclear complex [{Ru(bpy)2 }{Ru(phen)2 }{Ru((CH3 )2 bpy)2 }(µ-HAT)]6+ {the subscripts b. In many cases. 3.40–42 The Chiragens CG[n] where n > 4 show stereospecific coordination to the octahedral metal centers ruthenium and osmium. an example of which is illustrated in Figure 10(b). which are predominantly cationic.28 3. b p m /b p m .4 Stereospecific synthesis—chiral building blocks and the “chiragens” Ru(bpy)2 Figure 7 Stereoselective synthesis of diastereoisomers of alkyne-bridged trinuclear species. m-. Ltd.39 or o-.5. the combination of the stereoselective and chromatographic techniques has been used for the separation of stereoisomers of dinuclear and trinuclear species. 4–7}. and the enantiomers of the homochiral form subsequently resolved by chromatographic methods.27 The enantiomers of the heterochiral trinuclear species were obtained by reaction of the chromatographically resolved forms of the rac diastereoisomer of the dinuclear complex [{Ru(pp)2 }2 (µ-HAT)]4+ ( and ) with racemic [Ru(pp)2 Cl2 ] and then chromatographically separating the resultant 3 /2  (or 3 /2 ) product mixtures. The technique has allowed the routine separation of diastereoisomers.31 3. p. Importantly. these diastereoisomers were separated chromatographically. ∗ . the resolution of enantiomers. or p-xylendiyl {denoted CG[o/m/p-xyl]}. The underlying principle of stereospecificity is that a chiral precursor metal center will impose stereochemical identity on the other metal centers in oligomers derived from it. ∗ . von Zelewsky and his coworkers achieved the “chiralization” of the bidentate bpy ligand by functionalization with the naturally occurring chiral species (−)-myrtenal.27 However. it is important to note that the products are almost invariably homochiral.8. The linkages used have included an alkyl chain {denoted CG[n].4. following the synthesis of a mixture of the homochiral and heterochiral forms (Figure 9) using the racemic [Ru(pp)2 (CO)2 ]2+ precursor.37 and the same ligands have been used to control the stereochemistry of the general species of the type [Ru(CG[n])Cl2 ] and [Os(CG[n])X2 ]m+ (X = Cl− . and ∗ forms of the homoleptic heteronuclear species [{Ru(bpy)2 }2 {Os(bpy)2 } (µ-HAT)]6+ (where the asterisk refers to the Os center). for the trinuclear complexes involving the ligand 1. 37 giving rise to the chiral [4.1. 43 which may be used as precursors in the syntheses of higher nuclearity assemblies. This procedure was extended to the isolation of the ∗ .36. This article is  2012 John Wiley & Sons. the separation of geometric isomers. ∗ . Online  2012 John Wiley & Sons. n = 0. access to the heterochiral analogs requires the additional use of chromatographic techniques. phen. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. and the isolation of the eight stereoisomeric forms (b p m /b p m . the stereoselective synthesis using the chirally resolved forms of [Ru(pp)2 (CO)2 ]2+ gave rise to the enantiomers of the homochiral forms of the species [{Ru(pp)2 }3 (µHAT)]6+ (pp = bpy or phen).smc015 .33–35 have provided a cation-exchange strategy in which the eluent counteranion has been chosen so that it differentially associates with the stereoisomers to be separated. X = DMSO. Ltd.2 -bipyridine ligand shown in Figure 10(a). Ltd. (CH3 )2 bpy (4.5]-pineno2.4 -dimethyl-2. Supramolecular Chemistry: From Molecules to Nanomaterials. and the separation of chiral helical forms.12-hexaazatriphenylene (HAT). m = 2). These ligands undergo a regioselective deprotonation whereby two such moieties may be linked by a spacer to give the “Chiragen” series of tetradentate ligands.3 Heterochiral systems—combining stereoselective synthesis and chromatography In the examples reported on the use of the stereoretentive methods (including those cited above).2 -bipyridine)}.1002/9780470661345. ∗ .

Chirality Ru(bpy)2 2 Λ-[Ru(bpy)2(py)2]2+ H N H N N N Ru(bpy)2 4 Λ-[Ru(bpy)2(py)2]2+ H N H N N N 2+ N − N N − N + 7 H N H N N N (ΛΛ) + Ru(bpy)2 4+ Ru(bpy)2 N − N N − N − N N − N N Ru(bpy)2 Ru(bpy)2 Figure 8 (Λ4-Ru) Stereoselective synthesis of homochiral tetranuclear complex incorporating the bridge bis(2.32 (a) (b) Figure 9 Chem 3D representation of diastereoisomeric forms of [{Ru(bpy)2 }3 (µ-HAT)]6+ : (a) heterochiral {}.2 -bibenzimidizole). This article is  2012 John Wiley & Sons.1002/9780470661345. Online  2012 John Wiley & Sons. Supramolecular Chemistry: From Molecules to Nanomaterials. Ltd. N N − (CH2)n − X= N N (a) N N [X] CH2∗ ∗ CH2 ∗ H2C N N CH2 (b) Figure 10 Chiragen ligands: (a) [4. and (b) an example of a tetradentate Chiragen ligand.5]-pineno-2. Ltd. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. DOI: 10. one of the chiral building blocks of the Chiragen ligands.smc015 . (b) homochiral {(≡ )}. Ltd.2 -bipyridine.

which are ideal for the formation of double-stranded helicates with (a) (b) Figure 13 (a) A schematic representation of a trimetallic double-stranded helix (formed using a tri-bidentate strand with tetrahedral metal centers.1002/9780470661345. The name helicate was proposed to specifically refer to helices formed using interactions between metal centers and appropriate ligands. DOI: 10.. The observed chirality in helicates can arise from the inherent asymmetric spiral arrangement of the molecular components. Supramolecular Chemistry: From Molecules to Nanomaterials.43 A Chiragen based on the “dipineno” precursor (Figure 11a) has also been developed {designated superchiragen[0] or SGS[0]} (Figure 11b) and shows similar behavior to its CG[0] analog. such as the ligand shown in Figure 15) by appropriate spacers leads to extended chains. Ltd. 3) and the CG[bpy] do not coordinate as tetradentate ligands: however. They have been incorporated in di.10-phenanthroline—such as the ligand shown below in Figure 14) with appropriate spacers will produce extended chain ligands that allow the formation of double-stranded helices when the metal centers are tetrahedral (Figure 13a). and the pitch is the distance between two turns (Figure 12). This article is  2012 John Wiley & Sons. 44 4 HELICATES The helix is a motif prevalent in chemistry and biology—the “Crick and Watson” canonical double helical structure being but one of many well-known examples. In all examples. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. In a similar manner. and (b) a dimetallic triple-stranded helix (formed using a di-bidentate strand with octahedral centers). As shown in the schematic diagram in Figure 13. the connection of two (or more) tridentate units (e.or trinuclear species: in such systems stereospecificity was observed. and the “superchiragen[0]” ligand (b). they coordinate to a metal center in a bidentate manner and therefore are potential bridges.39.2 -bipyridine or 1. showing the pitch of metal center which ultimately controls the supramolecular architecture. The P and M helical forms. The chirality is defined by whether the screw sense is described by the right hand (the fingers indicate the direction of the screw progressing the helix in the direction of the extended thumb) or the left hand—designated plus (P ) or minus (M). Ltd.2 -bipyridine (a).5]-dipineno-2. induced by the chirality of the metal centers involved. even if the building blocks are achiral. the connection of two or more bidentate coordinating units (often 2. but triple-stranded helices when the metal centers are octahedral (Figure 13b). or a tri-tridentate strand with octahedral centers). This is discussed below with a limited number of illustrative examples. terpyridine. and it has been substantially reviewed.smc015 . or alternatively. a helix is associated with a sense of the screw around the helical axis—in which case it is chiral. The ligands CG[n] (n = 0. respectively. 43 The tetradentate Chiragen ligands have made a significant contribution to the transfer of chirality in metallosupramolecular synthesis.8 Concepts N Pitch N N N N N (a) (b) M P Figure 11 [4. it may result from the use of chiral bridging agents so that the chirality is transferred to the coordinated Figure 12 a helix.g.14. Ltd. Online  2012 John Wiley & Sons.

49 There have been a significant number of examples of triple-stranded helicate structures. homochiral helices have been observed. the product will be a racemate but almost invariably each helix will be homochiral. Ltd. oligo(1. using an eluent with a chiral anion. such as an oligoterpyrine (Figure 13a).46 Again. the octahedral bis(tridentate)iron(II) component centers are configurationally achiral. using octahedral metal centers and ligand strand containing bidentate coordinating groups (Figure 13b). and involved chains of oligobipyridine ligands linked by the tetrahedral coordination center Cu(I): an example is shown in Figure 14 of the product formed in a self-assembly process. the two enantiomeric forms were separated by cation-exchange chromatography.to hexanuclear species. and there are many examples of double-stranded helices of this genre. the original examples were reported by Lehn et al.3-oxazoline rings is asymmetric—an enantiomerically pure trinuclear circular helicate was formed with Ag(I) in which the metal centers are di-coordinated. but tetrahedrally coordinated) is shown in Figure 17(c). Online  2012 John Wiley & Sons.46 In virtually all examples where crystal structures have been performed. 49 (Figure 15). This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. oligo(pyridine/ imine).smc015 . and other heterocyclic donors.47. in cases where the ligand is configurationally nonchiral. have been used. positive cooperativity is thought to occur to realize the homochiral helix. Where octahedral centers are involved. double-stranded helical structures may be formed using chains with repeating tridentate units.14 Subsequent studies by numerous research groups have produced many other analogous examples.50 In a case involving the Chiragen ligand shown in Figure 17(b). and a series of chain ligands containing various combinations of pyrimidine.47 4+ N N N N N N N N Figure 15 N Fe Fe N N N A dinuclear double-stranded Fe(II) helix. Ltd. DOI: 10. 46 and only some illustrative examples are given here. 48 metal centers that prefer an octahedral geometry (for which Figure 13a is appropriate). but obtained as racemates given the achiral nature of the components. In general.1002/9780470661345. 46 These involve a cyclic arrangement of the metal centers. 9 In terms of double-stranded helices. it is possible to obtain only one of the helical isomers by spontaneous separation during crystallization.45 However. This article is  2012 John Wiley & Sons. with bridging ligands that loop around the metals and connect them: in the case of the di. although some additional cases exist where particular structural features of the spacers between the coordinating motifs. A simple example is the di-iron double helicate formed by self-assembly upon reacting Fe(II) and the appropriate ligand in equimolar proportions48. Supramolecular Chemistry: From Molecules to Nanomaterials.10-phenanthroline). where oligo (catechol).14.47 Other analogous longer (and shorter) double helices have been reported. where nonchiral ligand chains are used.Chirality N N N Cu+ N N N O O O N N 3 Cu(I) 2 N Cu+ N N N O OO N N N Cu+ N N N Figure 14 A trimetallic double-stranded helix Cu3 L2 (formed using a tri-bidentate strand) with the tetrahedral Cu(I) metal centers. Similar to the bis(bidentate)copper(I) centers in the earlier examples. a hexanuclear circular helicate formed51.46 In this particular instance above. Accordingly. or specific effects such as π –π stacking within the chains. benzimidazole. a particular twist may be induced on the resultant helicate. Ltd. There are many examples of doublestranded and triple-stranded helicates reported which will adhere to the above principles. Circular-stranded helicates have also been reported. generally formed by selfassembly. 52 (again with Ag(I). have given rise to additional features: this has been extensively reviewed14. helicates will usually be formed as a racemic mixture of the two homochiral enantiomers: in rare circumstances. by incorporating chiral substituents on the ligand chain. In the case of the ligand shown in Figure 17(a)—in which a carbon atom of each of the 1. the trinuclear and hexanuclear species (see Figure 16) have been involved in cases where the chirality has been addressed. imidizole. the molecule forms as a racemic mixture of the two chiral helical forms.

This article is  2012 John Wiley & Sons. Ltd. with complete enantioselectivity.6]-Chiragens. 51. form well-defined assemblies with octahedral metal centers. the related [5. Ltd.6]-Chiragen ligand used in the formation of hexanuclear helicate M6 L6 {M = Ag(I) or Cu(I)}. the single-stranded circular hexanuclear helicate results. The resultant metal-coordinated species (called a catenate) was subsequently demetallated to form the catenane with two interlocking macrocyclic rings. in the case where nonsymmetrically substituted phens are utilized (such as in Figure 20b).51 (Figure 17(c) reproduced from Ref.1 CATENANES AND MOLECULAR KNOTS Catenanes One of the significant developments in the field of supramolecular chemistry in the last two decades has been the formation of catenanes (interlocked rings) and molecular knots. Ltd. (b) [5. However.14. Zn(II). DOI: 10.57 Supramolecular Chemistry: From Molecules to Nanomaterials. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. 52 . The dominant strategies have involved the templating action of a tetrahedral Cu(I) center to two bidentate phen-type ligating moieties—incorporated either in two open chains that could subsequently be end-joined (generally using a di-iodo derivative of pentaethylene glycol) to give the interlocked rings. using the [4. For the simple case with the symmetrical phen-containing threads. and for this ligand with a p-xylyl spacer with tetrahedral ions such as Ag(I) or Cu(I). The former strategy is shown in Figure 19 for the simplest example of a [2]catenane. the resultant [2]catenane is nonchiral.  Wiley-VCH. with complete enantioselectivity51. and Fe(II) the major species formed are triple-stranded helicate species.6]-Chiragen N [Bridge] N [Bridge] BRIDGES: (a) p -Xylyl (b) Figure 16 Schematic representations of a trinuclear circular helicate (a) and an hexanuclear circular helicate (b). N N Ph O Figure 18 m -Xylyl [4. with Cd(II). 1998.10 Concepts N [4. or with one incorporated in a previously formed ring through which an open ring was threaded followed by subsequent closure.5].5]-Chiragen N N N N N [5. and do not 5.55 although other groups have since expanded on the theme.53 However. 51.smc015 .) The control of the chirality in the formation of helicates by the use of chiral ligands is demonstrated clearly by these tetradentate Chiragen ligands. The concepts were initially developed largely through the work of Dietrich-Buchecker and Sauvage. such as shown in Figure 20(a).44.6]-Chiragens (Figures 17b and 18) are somewhat more sterically demanding.and [5. (c) crystal structure views of hexanuclear helicate [Ag6 (L)6 ]6− . and in this case the catenate formed (shown on the left of Figure 20c) was shown to be chiral using 1 H NMR in the presence of a chiral reagent. 44 As a particularly illustrative example. 54 N N 5 N O (a) Ph N N (b) (c) Figure 17 (a) Ligand used in the formation of trinuclear circular helicate AgI3 L3 50 . which have an M2 L3 stoichiometry with enantiomerically pure structures.1002/9780470661345. which has been substantially reviewed. the resultant catenane is chiral. Online  2012 John Wiley & Sons.5]-Chiragen bearing an m-xylyl spacer (Figure 18).

58 5. but has been discussed in the literature.56. DOI: 10. the catenane has topological chirality. Ltd. 56. 56.57 (Reproduced from Ref.) OH OH N N N N (a) OH (b) OH O O O O O O O O N O N O O N Cu O N N + O N N O N O O O O O O O O O O (c) Figure 20 (a) A symmetrical bidentate chelating ligand used in the formation of catanates/catenanes. 1993. Online  2012 John Wiley & Sons. (b) the nonsymmetrically substituted phen-containing ligand used in the formation of the chiral catenate (c.58 have characterized such molecules as “molecular rubber gloves. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. Ltd.smc015 . plane. (Reproduced from Ref.3 Higher catenanes and molecular knots When the strategy shown in Figure 19 is extended to higher catenane analogs and to molecular knots. in instances where the molecule is chiral albeit being subject to deformation in 3D space. and racemization cannot be achieved without the breaking and reforming of chemical bonds. The U-shaped fragment contains a bidentate coordinating moiety. and the reader is directed to those reviews. additional Supramolecular Chemistry: From Molecules to Nanomaterials. or stretched rather than broken—the concept of the  and  forms of tris(bidentate) metal complexes being theoretically interconverted by the trigonal (“Bailar”) twist through an achiral (D3h ) trigonal trismatic transition state is a simple example. Chambron et al. on the left) and its catenane (right). compressed. This article is  2012 John Wiley & Sons.” in the sense that removing a right-handed glove from the right hand by peeling it off while turning it inside out results in an object which is superimposable on a left-handed glove—but at no point did the glove ever attain an achiral conformation.  Springer. or improper axis of symmetry (as discussed earlier in Section 1).1002/9780470661345. Clearly in the case. However.  Springer. Ltd.Chirality − Cyclization + 11 2 Figure 19 Template synthesis of a [2]catenane. The normal (Euchlidian or geometric) definition of chirality is based on the nonsuperimposability of rigid molecular objects: in symmetry terms this means that these forms do not possess a center. 1993.) 5. and the black dot represents a tetrahedrally coordinating metal ion. Such chiral forms may be theoretically interconverted by pathways in which bonds are bent. In a useful analogy.2 Topological chirality The nature of the chirality in the case of this catenane is notable as it raises the concept of topological chirality. the concept of topological chirality results in which the mirror image forms only by a chiral pathway. This concept will not be further dealt with in this chapter.

Ltd. and only the one resulting from the P-R and Q-S end-closures—the trefoil knot—is (topologically) chiral (the two chiral forms are shown in Figure 22). the methodology requires the formation of a molecular thread. a tetrahedron has T symmetry). Ltd.g. 6 Figure 22 Topologically chiral forms of a trefoil knot. For example. 56. or as a consequence of the coordination mode the ligands adopt relative Supramolecular Chemistry: From Molecules to Nanomaterials. are joined by the copper(I) centers giving only one chiral form of the double-stranded helix (II). in the formation of the simplest knot—called a trefoil knot —the strategy involves the use of threads containing two bidentate coordinating groups.  Springer. The appropriate connection affords the trefoil knot enantioselectively.59.) chirality considerations arise. CHIRAL POLYHEDRA A number of supramolecular polyhedra are chiral. and the topological chirality of the demetallated species was confirmed by NMR studies using a chiral shift reagent. Two of the di-bidentate chains used in this methodology are shown in Figure 23.smc015 .12 Concepts −2 PR + QS P R Q S −2 PQ + RS PS + QR −2 Figure 21 The three possible connections between the four ends of a dimetallic double-stranded helicate.1002/9780470661345. which is helical and therefore inherently chiral and which can be linked as described above for the [2]catenane. 60 A related chiral di-bidentate Chiragen chain has also been exploited to form stereoselectively determined molecular knots. This article is  2012 John Wiley & Sons. As shown in Figure 21. Using an m-phenylene (a) {rather than an n-butyl (b)} linkage between the phenanthroline moieties. Online  2012 John Wiley & Sons. Ltd. the resulting di-copper knot was resolved using diastereoisomer formation with a chiral anion. (Reproduced from Ref. There are three possible outcomes. sometimes because of the dissymmetric property of the shape itself (e. 1993.61 The molecular thread I (shown at the left in Figure 24) incorporates two bidentate chelating units: two N N N N OH OH OH (a) N N N N (b) OH Figure 23 Di-bidentate ligands used in the formation of doublestranded helicates with tetrahedrally coordinating metal centers. DOI: 10. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons..

which possess T point group symmetry. 65 . four octahedrally coordinating metal centers were connected by six di-bidentate ligand strands (M4 L6 . N N N 6. di-bidentate ligands based on catecholate bidentate coordinating entities (c)66 . This area has been well documented in two recent book reviews62. 68 . Online  2012 John Wiley & Sons.Chirality N this chapter will draw attention to the principles involved with a few illustrative examples.65 O O O O O Figure 24 Formation of a chiral trefoil knot using a Chiragen ligand.) to the metal centers that form the polyhedron. In an example using the ligand shown in Figure 25(b(i)). Ltd.64 Interestingly. X-ray structural studies showed that a tetrahedral complex Co4 L6 involving four Co(II) centers was formed as a racemic mixture of homochiral  and  enantiomers.  Wiley-VCH.61 (Reproduced from Ref. 2004. di-bidentate ligands containing the pyrazolyl-pyridine coordinating group. in a complex of the same M4 L6 formulation involving the related ligand shown in Figure 25(b(ii)) and Fe(III) as the metal center. Ltd. In these first examples. with a series of linkers (d)67. developed in situ during the reaction.1 O 13 Tetrahedra O O Much of the seminal work in this area has been done by Saalfrank and coworkers. Ltd. 63 : O O − OR CO2R O OH HN CO2R O − OH HN OR O O (i) O (a) (b) OH O − HO OCH3 O CO2CH3 − O CO2CH3 (c) (i) (ii) (iii) OCH3 (ii) ∗ ∗ N N N N N ∗ (d) N N ∗ ∗ ∗ ∗ ∗ ∗ N N N ∗ (e) Figure 25 A schematic representation of the tetrahedral supramolecular assembly M4 L6 with four octahedrally coordinating centers linked by di-bidentate ligands (a): di-bidentate ligands involving “acac”-type bidentate coordinating entities (b)64.smc015 .1002/9780470661345. Figure 25a).69 Supramolecular Chemistry: From Molecules to Nanomaterials. This article is  2012 John Wiley & Sons. rather than attempting to be comprehensive. 61. DOI: 10. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. X-ray crystal studies revealed the formation of a tetrahedral metal core with an achiral meso configuration . and by Raymond and coworkers. a quaterpyridine ligand (e).

In this case.74 Ward and coworkers reported a series of Co4 L6 complexes involving the series of di-bidentate ligands containing the pyrazolyl-pyridine coordinating group shown in Figure 25(d).67. and this research group was able to resolve the racemic mixture of Ga4 L6 .69 Raymond et al. reaction with Fe(II) forms an Fe4 L6 tetrahedron. but as shown in the schematic representation in Figure 27(b). was found to be remarkable. with tri-β-diketonate species (iii). again incorporating simple anions. while one pair of ligands share one metal each for coordination of their central pyridine groups (shown in Supramolecular Chemistry: From Molecules to Nanomaterials.73 and (iii). N N N N N N N N N (a) (b) Figure 27 (a) Tridentate ligand used by Fujita et al. However. investigated by 1 H NMR. they are isolated examples and the homochirality arises either from the asymmetric orientation of the ligands in the framework. DOI: 10. for the quaterpyridine ligand. This article is  2012 John Wiley & Sons. 70 For the quaterpyridine ligand shown in Figure 25(e). where L is the ligand shown in Figure 25(c(i)).73 and Raymond. The ligand adopts a facial coordination to the octahedron.72 Raymond et al.66 The configurational stability of this species. in which simple anions were incorporated in the cavity. Ltd.2). and when the ligands were manipulated to enlarge the cavity in the tetrahedron “cage” that cationic guests could be encapsulated. Interestingly.76 The six metal centers involve the Pd(L2 ) moiety.71 There are also a series of tetrahedral assemblies with the formulation M4 L4 .62 An interesting example of a chiral octahedral cage M6 L4 was reported by Fujita et al. Three examples of such ligands are shown in Figure 26(b): Ward et al. Saalfrank et al. the three octahedrally coordinating metal centers on any face of the tetrahedron of metal centers are jointed by trigonally symmetric tribidentate “tripod” ligands. reported the self-assembly of a series of di-bidentate catecholate ligands (Figure 25c) with a number of trivalent and tetravalent metal centers to produce chiral M4 L6 tetrahedra.14 Concepts OH BuO N N N N O CO2Bu O N N HO (b) (i) CO2Bu O OH OBu OH (a) OBu HO HO O N O N H HN HO O BuO2C NH B N N OH OH (ii) (iii) Figure 26 A schematic representation of the tetrahedral supramolecular assembly M4 L4 with four octahedrally coordinating centers linked by tripodal ligands containing three di-bidentate entities (a) examples of the tripodal ligands. reaction with RuCl3 under reducing conditions formed a [Ru2 L3 ]4+ helix (of the type shown in Figure 13b). Ltd. (b)—(i). using the chiral (−)(S)-methylnicotinium cation as a guest. involving the tridentate ligand shown in Figure 27(a).smc015 . the assembly is formed as a racemic mixture of homochiral  and  enantiomers. using tri-catecholate tripod (ii). Ltd.1002/9780470661345.68 In all these examples. for which the enantiomeric  and  forms were separated using a cation-exchange technique described earlier using a chiral eluent containing the anion (−)-O.76 to form the chiral octahedral cage shown in (b).75 6. Each of the metal centers has octahedral tris(bidentate) coordination. the structures possess a cavity. or where the achiral framework is rendered dissymmetric by the encapsulation of a guest. with exclusive formation of a racemic mixture of the homochiral arrangements. reported M4 L4 assemblies with tris(pyrazylpyridine)borate (i). shown schematically for one such ligand in Figure 26(a). Online  2012 John Wiley & Sons. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons.2 Trigonal (anti)prisms and octahedra There are limited examples of chiral trigonal prismatic and antiprismatic assemblies: in general. where L2 is a bidentate ligand bpy or en.74 It is noted that the metal centers at the vertices of the tetrahedra were homochiral.O  -dibenzoyl-l-tartrate (Section 2.1. where the  enantiomer preferentially precipitated as the least soluble diastereoisomeric form.72 (ii).

forming a triangular face of the cuboctahedron. Ltd. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons.1 -binaphthyl-6. This article is  2012 John Wiley & Sons. DOI: 10. and four trithiocyanurate anions Chiral molecular polygons Lin and coworkers have reported a detailed study using chiral bridging ligands to generate chiral polygons. are linked so that each TCA3− combines with three Zn-cyclen moieties from separate complexes. 79 These rigid atropisomeric ligands—such as shown in Figure 29(a)—were reacted in enantiomerically pure form with trans-[Pt(PEt3 )2 Cl2 ] to produce a range of chiral Supramolecular Chemistry: From Molecules to Nanomaterials.1002/9780470661345.3 (TCA3− .77 The cuboctahedron—shown in Figure 28(a)—has eight triangular and six square faces. Ltd. and (b) the n = 4 chiral polygon derived from it using the trans-Pt(Et3 )2 linker. Chiral induction was achieved by encapsulation of a chiral guest molecule. (b) the tripod ligand.smc015 . There is a rotational offset imposed and this twist (either clockwise or anticlockwise) renders the assembly chiral. Cuboctahedra 6. The resultant octahedral structure has C2 point group symmetry and is therefore dissymmetric. Online  2012 John Wiley & Sons. In the structure. Ltd. Figure 28c). 79 red in the diagram).4 In the final example of the polyhedra. 6. and (c) trithiocyanurate anion (TCA3− ) linker used in the formation of the chiral cuboctahedron. four complexes involving three Zn(II)-containing cyclen macrocycles (Figure 28b) attached to a phenyl ring.77 PEt3 AcO OAc OAc Pt AcO PEt3 R Et3P R Pt PEt3 Et3P Pt PEt3 (a) PEt3 AcO Pt AcO PEt3 OAc OAc (b) Figure 29 (a) 2.78. the other two ligands have their central pyridine groups coordinated to trans-disposed metal centers (shown in purple). with the three particular metal centers having a meridional disposition.6 -bis(ethyne).78.2 -diacetyl-1.Chirality 15 NH HN N HN HN NH N NH S− N NH = (a) HN N H N Zn2+ − (b) S N N S− (c) Figure 28 A (a) cuboctahedron. an example of distorted octahedron has been reported.

Ltd. These examples have been well covered in excellent reviews and other books which are cited in the text and/or are listed in the “Further Reading” that concludes this chapter. 81 A similar methodology was also employed with the related series of di-pyridine ligands shown in Figure 30. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. the chiral complex shown in Figure 32(a) {M = Pd. or have minor variations from them.86.1 -binaphthyl framework. This article is  2012 John Wiley & Sons.83. the size and shape—and nature—of which can be controlled by appropriate manipulation of the components.6-diazaanthracene realized a single diastereoisomer of the square shown in Figure 32(c). Pt. an example of which is shown in Figure 31(b). which act as templates in the actual initial construction of the assembly. and the cavities of formed assemblies can clearly be used as host centers. and (b) a chiral metallocycle derived from one of the ligands in (a) with M(en) as a linker {M(II) = Pd or Pt}. Online  2012 John Wiley & Sons. Ltd. so that for guest molecules there are consequences associated Supramolecular Chemistry: From Molecules to Nanomaterials. 87 7 CONCLUSIONS This chapter has attempted to provide a basic insight into some of the principles involved in chirality in metallosupramolecular chemistry.82 The further incorporation of a chiral backbone into these di-pyridine ligands (Figure 31a) was also used to prepare chiral supramolecular species. H 2N N CH3O CH3O O N NH2 4+ N CH3O OCH3 CH3O OCH3 N N H 2N O (a) M N M NH2 (b) Figure 31 (a) Angular di-pyridine ligands with chiral backbones.84 A related reaction involving the alternative bridge such as 2. 84 metallo-macrocyles of different sizes (n = 3–8. The enticing logical prospect is that in a chiral assembly the cavities have inherent chiral characteristics. One of the pervasive outcomes of the development of supramolecular chemistry is that the assemblies possess cavities. DOI: 10. OTf− = trifluoromethanesulfonic acid anion (triflate)} can be treated with the bridging ligand bis[4-(4 -pyridyl)phenyl] iodonium triflate to produce the chiral square shown in Figure 32(b). Ltd. the product with n = 4 is shown in Figure 29b).80. This strategy was subsequently extended to produce a series of chiral mesoscopic macrocycles of controllable size. 84 Stang et al. proposed a number of strategies to create chiral supramolecular assemblies in self-assembly processes.85 By way of examples.83. without the distraction of being dispassionately inclusive of the myriad of examples that support those principles.1002/9780470661345. “Procavities” are sometimes used by species.16 Concepts N N N Cl RO RO RO RO RO RO Cl N N N Figure 30 Angular di-pyridine ligands based on the 1.smc015 .

and so the further incorporation and exploitation of the chiral environment in metallosupramolecular chemistry promises to be one of the most exciting aspects of nanoscience in the immediate and intermediate future. J. A. N. Topics in Current Chemistry. A. Yeh. 7.smc015 . This article is  2012 John Wiley & Sons. eds.. 2. V. Ltd. Online  2012 John Wiley & Sons.Chirality 17 6+ PHPh2 P M N Ph2 N Ph P P Ph Ph M Ph OTf N OTf I+ N N I+ N N Ph2 N M P Ph2P (a) (b) 8+ Ph2P PPh2 M N N N N P M P P M N N P N N M Ph2P PPh2 (c) Figure 32 (a) Chiral metal building unit [M(R-(+)-BINAP(OTf)2 ] {M(II) = Pd. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. REFERENCES 1. Supramolecular Chemistry: From Molecules to Nanomaterials. Oxford. Crego-Calama and D. Reinhoudt. Meyer. Ltd. DOI: 10. McCleverty and T. in Comprehensive Coordination Chemistry II. 2003. eds. vol. N. Supramolecular Chirality. Inc. Pt} used by Stang and coworkers to produce a chiral supramolecular squares (b)86 and (c). J. John Wiley & Sons.1002/9780470661345. Elsevier. Davis. asymmetric catalysis.” but they will also be expanded within this present series. M. The possibilities in terms of the design of metallosupramolecular species are limited only by the imagination. and nanoscience applications such as “Molecular Machines”—just to name a few. Raymond. Chichester. 2006. 87 with chiral host environment. surface interactions. 265. M. and K.86. p. R. Ltd. Some of these concepts are discussed in articles included below in the “Further Reading. vol. 327. It follows that there are potential applications in areas such as asymmetric sensing.

T. 10364. 6. D. M. Harper. E. F. Chem. Monlien. F. and J. Northop. 1999. J. Chem. vol. Acc. 33.. D. Rev... 1996. 2009. A.. Dalton Trans. J. 1964. Champin. J. von Zelewsky. Fletcher and F.. 55. J. 219.A. A. Nord´en. O. Z.. Top. A. Chem. Belser. Inorg. Angew. 8. 37. 972. R. Chim.. A. Coord. 1542. 1987. Lehn.. Chem. J. Rutherford. R. Int. Am. Dalton Trans. 701.. Sci. O. 32. N. Am.. Chem. 38. P. eds. Engl. Dwyer and D. Yin and R. Stoeckli-Evans. 1993. Chem. 58. Keene. Coord.-C. O. Chem. Gunde. X. 1996. 48.. B.. F.. H.. Stang. Fletcher. J. 121. 166. DOI: 10. U. Hiort. Chem. Coord. 47. 37. Mamula and A. Stang. Chem. Patterson and F. Sargeson. von Zelewsky.-P. 4. S. Topics in Current Chemistry. 38. 12. 35. Chem.. J. Viebrock. 1998. Mellor.. J. 1996. T.. A. 7. 795. 36. 242. 3049.-M. and F. Inorg. V.. Dalton Trans. A. 1997.. K. Rutherford. Caulder and K. Chem. Helv. P. and J. 133. Rev. 249. Mamula. A. 118. J.. et al. Rivera-Minten.. and F. J. et al. Chambron. 1999. Chem. Supramolecular Assemblies and Materials.-C. 100. C. Chichester. 46. Chem. R. Soc. Venturi. et al. Hewage. Thomas. Inc. H. Keene. and A. L. Soc. Chem. A. Natl. F.. Hayoz. 2007. Torres. 1999. 2565. 426. 22. C. A. Chem. Chem. M.. Chem. and F. H. 1996. 2003. 84. Academic Press. 2145. 21. Commun. N. Patterson. D.. Stereochemistry of Coordination Compounds.. Lehn.. 37. T. A. Sauvage. Chem. Rev. B. Quagliotto. Soc. MacDonnell and S.. Engl. Rev. Springer Verlag. 56. Sauvage. A. Rutherford and F. F. Mobian. 709. 42. 34. A. Tor.. J. 1802. Mamula. in Chelating Agents and Metal Chelates. 1971. 15. S. Soc. Richards.-R. et al. P. Optical phenomena in metal chelates. Chem. M. P. 5111. von Zelewsky. Sauvage. 2001. Balzani. and J. 1998. C.. Inorg. Bodige. 25.. J. Ltd.. Ed. Chem. and M. 7.. Am. B. D. 5791. Chem. von Zelewsky. 5. H. Keene. 358. Inorg. Fletcher. Amouri and M. Rigault. T. New York. Olenyuk. 43. von Zelewsky. and F. A. Chambron. F. 1995. Chem. 23. R. Rapenne. von Zelewsky. vol. Chem. 2008. L. 7989. ed.-P. L. Soc. 1155. 115. Inc. 2005.. R. R. A.. 1997. Chem.. Tetrahedron Lett. Dietrich-Buchecker and J. Chem.—Eur. 5165.. Soc. 26. 852.. Inorg. M. and P. Inorg. 249. Angew. and H. Sauvage. S.. Tzalis and Y. R. 683–689. 32. Patterson. Rev.. Keene. Chem. Keene. Chem. von Zelewsky. R. A. 1996. 185. Rev. Hayoz.smc015 . 1997. Zheng. Lincoln. C. Chem. H. 132. 2000. Acta. and H. C. Foley. Soc. 3857. Soc. Chi. F. Online  2012 John Wiley & Sons. J. 45. 36. Chem.. Chem. John Wiley & Sons. J. Chem. 35. Inorg. Dalton Trans. Trans. 1994. 36.. E. S. 14. M. T. B. V. von Zelewsky. Junk. Rapenne. 1192.-P. 1554. 6. J. R. 1993. O. Rev. Buckingham and A. M. Soc. Mislow. Sauvage. 1988. C. 1996. and B. K. Watson. 6891. Eisenbaumer. 645. Chem. 1113. 2009. 1996. Chichester. P. Soc. 533. Chem. 119. 5. A. 1997. 201. 101. 2001. 1996. and F. Van Gijte. Credi. 11. J. This article is  2012 John Wiley & Sons. John Wiley & Sons. Mamula. Proc. Maurizot. Chichester. S. 5. 18. 115. 87. Ed. Inorg.. et al. 35. 87–95. R.. C. R. Rev.. T. Gruselle. 1992. Stoddart. 41. 19. and G. et al. Keene. 75. 121. Belser. Int. P. Dalton Trans. 1999. Soc.-P. Soc..-P. M. Kirsch-De Mesmaeker. 1996. Raymond. Chem. D.. 53.1002/9780470661345. 183–235. Jackson. 2001. M¨urner. 1998. 2006. Keene. Jandrasics. et al. Met. 34. 1998. Fletcher. J. P. 79. Acta. and A. Inorg. 3487. 4465. Soc. 3448. Nord´en. 1993. Commun. Hayoz and A. P. 2002. Keene. D. Ed. R. 930. Soc. R.-W. From classical chirality to topologically chiral catenands and knots. A. John Wiley & Sons. K. Chem. J. Inorg.. 5758. G. and M. Ltd. P. H. O. Chim.. Keene. 5. F. 924. Y. J. J. 2003. Provent. J. N. 13. 7. Mitchell and J. W¨arnmark. Chem.-M.-P. Inorg. C. Engl. J. 38. 1993. J. 50. J. J. Sauvage. Credi. M¨urner. 51. Lincoln and B. Dietrich-Buchecker and J. F. Dalton Trans. DeCian. 165. von Zelewsky. B. J. and P. 16. Fujita. pp. Hua and A. C. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. G. R. Res. Inc. K. 271. Rev. 33. Sauvage. Maloney. Am. Chem. J. Ltd. Ziegler. 3.. J. Am. von Zelewsky. 36. Soc. 42. M¨urner. Perspectives in Supramolecular Chemistry: Transition Metals in Supramolecular Chemistry.— Eur. 3931. 27. et al. Keene. Stoeckli-Evans. Am. M. 40.-R. Albrecht. J. 9. Kramer. 3457. 57. A. 29. J. and G. Keene. 1995. Chem. Heyke. 17. Int. J. 2009. 1966. 30. 853. Chem. et al. Chem. Res.-M. 44. 35. Bernardmelli. 54. M. Dietrich-Buchecker. O. von Zelewsky. 49.. Seidel and P. J. N.-P. 20.. J. 31. and J. 36. 303. J. et al. 2007. Hopfgartner. Yoshizawa. Stereochem. 709. 1998. 1997.. 289.18 Concepts 3.. 27. Leininger. O. Fischer. Siegel. A. J. Acta. T. P. Keene.S. Rev. Chem. Reitsma. C.. Lehn. 27. 1853. Top.. Chirality in Transition Metal Chemistry: Molecules. 1997. K.. and J. O. Sargeson. 11. P. J. 115. 1987. Dietrich-Buchecker. 36. Chem. 34. 39. von Zelewsky. 24. 4085. P. 277.-P.. 2005. 52.. E.— Eur. Bodige. 10. Porquet.. N. 2750. 1185. Sauvage. Sauvage.. G. Bridoard. Supramolecular Chemistry: From Molecules to Nanomaterials.. 28. 1999. 46. Acad. O. Chim.. B. C.. Chem. Angew. D. P. Stang. Curr.. 1999. Acc. Heidelberg.. D. Commun. Sargeson. R.. Chem.— Eur.

Xu. Angew. J. Ltd. et al. 5. J. 1993. Paul. Fiedler. 493. V. Chem. L. vol. Meehan. D. Chem. J. Stang. N. (a) M. Demleitner. 76. Chem. J. C.. Tiedemann. John Wiley & Sons. 34. Raymond. Dietrich-Buchecker. Int. Chem.. Pascard. Acad. Int. FURTHER READING M. S. 5. Chem. Soc.—Eur. Natl. Raymond. Saalfrank.. J. G. S. Terpin.. Ed. Ed. Olenyuk. Chapter 5. Inc. Ziegler. et al. 1995. Chem. 124. 75. 1995. K. eds. Soc. B. 2001. Supramolecular Chirality. 1993. Gruselle. 3094. Guilhem. 1179. Crego-Calama and D. H¨orner. C. 2002. 81. 10535. 8221. F. Lin. 8. ed. 78. 265.A. and K. Perret-Aebi. J. Yazaki. 5159. 14. N. Int. S. 1837. J... Sauvage. Ed. Jeffrey.-P. Raymond. Int. Organometallics. M. 1996. 43. 157. F.. Proc. S.. Ed.. B. N. Angew. Amouri and M. M. 1190. 2004. 2003. Clegg. P. Ogura. Chem. 1999. G. R. et al. Soc. 35. From Classical Chirality to Topologically Chiral Catenands and Knots.. Let’s Twist Again—double-stranded. Chem. J. 65. C. 86. within that volume. Chem. Chichester. J.. R. Chem. and K. P. Ed. Olenyuk. L. M.. C. R. and J. J. Dietrich-Buchecker. Kesanli and W.. et al.. R. 4883. Angew. Kimura. 38. 34. U.. 69. Int. Shin. Int. 87. 929. J. Aoki. 2006.S. DOI: 10. G. Acc. Jones. Chichester. Transition Metals in Supramolecular Chemistry: Perspectives in Supramolecular Chemistry. J. 246. 72. see G. Stalke.. Engl. Glasson. Chem. J. J. triplestranded. C. 127. K. Angew. Inorg. 75. Supramolecular Chirality in Coordination Chemistry. C. Chem. Muddiman. J. R. E. Y. R.. E. N. Engl.. vol. Inc. J. Gruselle. Chichester. Burak.—Eur.. B. H. Chem. et al. 2001. 1990. 62. 8084. Commun. 2002. von Zelewsky. Sauvage. 77. 5. Res. J. 732. Chem. and circular helicates. 43.. Sauvage. S. K. Lin. et al. Z. C. Leung. Raymond. 79. 63. C. W. 66. and K. Am. 1997. Olenyuk. Chem. et al. 40. Raymond.-P. Angew. 5645. 2005. Seeber. D. R. John Wiley & Sons. Chem. Chem. et al. W. 1432. Chem. H. 559. Bull. 70. 2005.-P. A. et al. Glasson. 3453. Chirality in Transition Metal Chemistry: Molecules. Inc. 118. Dietrich-Buchecker. Saalfrank. M.. Seeber. Int.. Inorg. Lin. J. This article is  2012 John Wiley & Sons. Bruckner. P. H. Sci. 85. B. 4482. J. 67. and K. Angew. 43. Angew. Supramolecular Assemblies and Materials. J. Bell. J. Lee and W. O. 73. Reinhoudt.... Am. B. Chichester.. V. Clegg. Raymond. Amouri and M. and K. Albrecht. 2002. E. John Wiley & Sons. 2004. Chirality in Transition Metal Chemistry: Molecules. 1999. A.. 4554. G. R. Seeber. 2008. Johnson. C. Powers. G. Inc. J. Ltd. and J. 2002. (b) with particular relevance to metallosupramolecular species. S. Ltd. C. et al. Inc. J. 305. Biradha. K. and E. 2008.. 2002. and W. B. This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons. 37. 2004. Chem. H. 2003. 125. 84. 8. Yeh. Stang.P. Glaser. Topics in Current Chemistry. Whiteford. 147–183. J. Angew.... 2005. H. 61. Jiang and W. P. M. J.-C. Coord. Chichester. N. J. 3457–3497. J. G. Springer Verlag. Dalton Trans. vol. Paul. Engl. 71. Y. Lin. 17672. and J. Ed. Lin. J. 993. Reihs. A.. Engl. Bergman. Ed. 44. C.—Eur. and P. 16. 2008. 1999. vol. R.. 74... Jpn. R. O. 80. 101. Chem. 6228. K. 99. 112. Engl. et al. E. Heidelberg. 21. Chambron. L. pp. Supramolecular Chirality in Coordination Chemistry. 60. J. Lee. N. H. Sauvage. Jeffery. Soc. 2004. Slabeck. Organomet. pp. Supramolecular Chemistry: From Molecules to Nanomaterials. Rev. 83. 690. Soc. P. Chem.1002/9780470661345. D. 6579. Jeffrey. U. Amoroso. John Wiley & Sons. Rapenne. W. Shiro.-S. and J. K. Argent. D. D.. 1443. Jeong. 2008. Fujita. Topics in Current Chemistry. Tiedemann. Fujita. C. Sauvage. 68.. Chem. 32. Chem. John Wiley & Sons. Chem. A. Jiang and W. 64. Soc. 1998. Ed. Am. Dietrich-Buchecker. Rev. S..—Eur. Meehan. 82. N.smc015 . W. Kubota. Supramolecular Assemblies and Materials. and K. 1996. R.. B. Online  2012 John Wiley & Sons. Kim. Am. Saalfrank. R. Am.Chirality 19 59.. L. Chem. 165. Int. S. Stang and B. 349. 4482. J.. and K.. Kim. 2005. 147–183.