8.

01 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays,

Coordination Polymers, and Assemblies
EC Constable and CE Housecroft, University of Basel, Basel, Switzerland
ã 2013 Elsevier Ltd. All rights reserved.

8.01.1 Introduction 1
8.01.2 Metallosupramolecular Chemistry 1
[Link] Hard and Soft Acids and Bases 2
[Link] The Chelate Effect 2
[Link] The Macrocyclic and Cryptate Effects 2
[Link] Metal-Binding Domains 3
8.01.3 The Synthetic Toolkit: Favored Conjugation Reactions 3
[Link] The Synthetic Organic Chemistry 3
[Link].1 The Suzuki reaction 3
[Link].2 The Stille reaction 5
[Link].3 Sonogashira coupling 5
[Link].4 Click chemistry 5
[Link].5 Schiff base chemistry 5
[Link].6 Grubbs’ catalyzed ring-closing metathesis 5
[Link] Template Reactions 6
8.01.4 Ligand Design for Macrocycles 7
8.01.5 Ligand Design for Coordination Polymers and Networks 10
8.01.6 Ligand Design for Metallopolygons 13
8.01.7 Taking Metallosquares into Three Dimensions through Ligand Design 16
8.01.8 Metalloligand Design 16
8.01.9 Ligand Design for Metal-Ion Extraction 20
[Link] Introduction 20
[Link] Copper 22
[Link] Gold, Palladium, and Platinum 24
[Link] Cobalt, Nickel, and Zinc 25
[Link] f-Block Metal Ions 25
[Link] p-Block Metal Ions 26
8.01.10 Conclusion 26
References 26

8.01.1 Introduction general introduction regarding the design concepts, concentrates

on a number of topics of current interest. We conclude the
Ligand design is at the core of contemporary coordination chapter with a short section on ligand design for metal extraction.
chemistry. Indeed, without ligands, there would be no coordi-
nation chemistry. It would certainly be possible to devote this
entire series of volumes to the topic of ligand design, and it is 8.01.2 Metallosupramolecular Chemistry
probably true to say that almost any conceivable atom, mole-
cule, or ion can act as a ligand in some circumstance or other. The basic precepts of metallosupramolecular chemistry are
Outstanding recent examples of ‘unusual’ ligands include simple.3,4 Mononuclear or multinuclear metal centers are used
xenon atoms,1 dihydrogen molecules,2 and CdH bonds.2 to assemble components into supramolecular structures. The
However, the aim of this chapter is not to highlight the exotic, components are bound to the metal centers by ‘metal-binding
but to attempt to provide guidelines for the design of ligands domains’ which are groups recognizable as ligands. Very often,
using a toolkit of ‘metal-binding domains.’ but not necessarily, the metal-binding domains are chelating
At the base of the design, concept is an understanding of the functionalities. The success of metallosupramolecular chemistry
factors which allow the selection of particular metal-binding lies in using the knowledge of coordination chemistry to match
domains for particular metal centers. These principles are at the the donor properties of the metal-binding domain (number,
core of metallosupramolecular chemistry and allow the design of type, and spatial arrangement of the donor atoms) to the accep-
optimized ligands for particular functional and structural roles. tor properties of the metal-containing components (number
This chapter can only give an overview of the enormous and spatial arrangement of available coordination sites). The
worldwide efforts invested in the design of ligands and after a key concepts for the design and matching of donor and acceptor

Comprehensive Inorganic Chemistry II [Link] 1

2 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

properties lie within ligand field theory and the hard–soft theory criterion of similarity of the donor atoms has been the subject
of acids and bases. of much debate in discussion of the origin of the chelate effect.7
Although originally interpreted in terms of a purely entro-
pic effect (three en ligands displace six water molecules so that
[Link] Hard and Soft Acids and Bases
the number of solution species is greater), more detailed ana-
The hard and soft acid bases (HSAB) model proposed by lyses show that this seductively simple explanation is neither
Pearson5 on the basis of a large body of earlier work classified general nor correct. To understand the thermodynamic origin,
metal ions and ligands as being either hard or soft, Table 1. As full consideration needs also to be given to solvation enthalpy
far as metal complexes are concerned, the model deals with and entropy effects in addition to the strain energy within
thermodynamics and states that more stable complexes will be the chelating ligands. This latter phenomenon is the origin
obtained from soft–soft or hard–hard interactions. of the observed 2–3 lg K units greater stability of 1,10-
The classifications arise from quantitative determinations phenanthroline (phen) complexes over 2,20 -bipyridine (bpy)
of the stability of complexes formed between appropriate analogs; effectively, the reorganization energy cost of bringing
Lewis acids and Lewis bases and provide a very good empirical the two nitrogens into the cis-configuration required for bind-
tool for optimizing ligand design. For ligands designed for ing the metal has been paid in advance in phen. In a way, the
palladium(II) centers, it would be appropriate to use soft important feature is phenomenological rather than analytical.
donors such as sulfur or phosphorus, while for metal ions When en is added to [Ni(NH3)6]2þ, ammonia will be displaced
such as sodium, a better choice would be a hard donor such with the concomitant formation of [Ni(en)3]2þ.
as an ether or negatively charged oxygen. In some cases, not all possible donor atoms are coordinated
Many attempts have been made to quantify what is essentially to a metal center and there has been much recent interest
a set of empirical rules. In soft acids, the acceptor atom has a zero in complexes containing hypodentate ligands,9 for example, a
or low positive charge and a relatively large size leading to low bidentate 2,20 :60 ,200 -terpyridine (tpy) ligand10 (Table 3).
electronegativity and high polarizability. Hard acids tend to be
more highly charged and/or small and are less easily polarized.
[Link] The Macrocyclic and Cryptate Effects
Soft bases are easily polarized with large donor atoms, whereas
hard bases have smaller donor atoms and are less easily polarized. In the same way that the linking together of donors to give
A convenient summary is to state that hard–hard interactions are chelating ligands results in the formation of more stable com-
‘more ionic’ and soft–soft interactions are ‘more covalent.’ It is plexes, so does the linking of donors into macrocycles. As with the
very important to remember that the HSAB model does not state chelate effect, the precise origin of the effect is still a topic of
that hard–soft interactions cannot occur, merely that they are less discussion, but the phenomenon is clear (Table 4). For a given
favored than hard–hard or soft–soft combinations. combination of donors, the most stable complexes are likely to be
formed with a macrocyclic ligand, subject to the constraint that
the optimal metal–ligand distances and optimal coordination
[Link] The Chelate Effect
geometry can be reached. The latter comments perhaps require
The chelate effect6 is a general and powerful design tool in a little clarification. The phthalocyanine ligand H2L1 usually
coordination chemistry that states that polydentate ligands coordinates in the doubly deprotonated form [L1]2– and presents
with two or more donor atoms will generally give more stable four nitrogen donors. However, although copper(I) is often four-
complexes than those with the appropriate number of mono- coordinate, this center cannot coordinate to the four nitrogen
dentate ligands containing ‘similar’ donor atoms (Table 2). The donors of [L1]2– because of their tetrahedral spatial arrangement.

Table 1 Classification of metal centers and ligands as hard or soft5

Description Metal center or group Ligand or donor atom

Hard Li(I), Na(I), K(I), Be(II), Mg(II), Ca(II), Sr(II), Sn(II), Al(III), Ga(III), In(III), H2O, OH–, F–, OAc–, PO43–, SO4 2 , Cl–, CO3 2 , ClO4  ,
La(III), Si(IV), Ti(IV), Zr(IV), Th(IV), Pu(IV), VO2þ, UO2 2þ , NO3  , ROH, RO–, R2O, NH3, RNH2, N2H4
Me2Sn2þ, Me3Al, Me3Ga, Me3In
Borderline Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Pb(II) ArNH2, py, N3  , Br–, NO2  , SO3 2 , N2
Soft Cu(I), Ag(I), Au(I), Tl(I),Cs(I), Pd(II), Cd(II), Pt(II), Hg(II), Hg2 2þ , MeHgþ, R2S, RSH, RS–, I–, SCN–, S2 O3 2 , R3P, R3As, (RO)3P,
Tl(III), Me3Tl, M(0) CN–, RNC, CO, alkenes, arenes, H–, alkyl

N
O
O O O O
O O
O O O O
O O O
O O
O O O O N
O

L4 L5 L6 L7
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 3

Table 2 Quantitative aspects of the chelate effect8

Reaction b DG (kJ mol1) DH (kJ mol1) DS (J K1mol1)

[Ni(OH2)6]2þ þ 6NH3 ¼ [Ni(NH3)6]2þ þ 6H2O 109 51.8 100 163

[Ni(OH2)6]2þ þ 3en ¼ [Ni(en)3]2þ þ 6H2O 1018 101.8 117 42

Table 3 Quantitative aspects of increasing the number of chelating completely encapsulate the metal center. These ligands are
donor atoms8 (D ¼ lg bdi/tridentate  lg bmonodentate) called cryptands and their complexes exhibit additional ther-
modynamic and kinetic stability over analogous open-chain
Reactiona lg b (lg K) D D (per compounds (Table 5).
donor)

Ni2þ(aq) þ 2py ¼ [Ni(py)2]2þ(aq) 3.10 [Link] Metal-Binding Domains

Ni2þ(aq) þ bpy ¼ [Ni(bpy)]2þ(aq) 7.04 3.94 1.97
The concept of a metal-binding domain is exceptionally sim-
Ni2þ(aq) þ 3py ¼ [Ni(py)3]2þ(aq) 3.71
Ni2þ(aq) þ tpy ¼ [Ni(tpy)]2þ(aq) 10.70 6.99 2.33 ple. Any group which can function as a donor set (monoden-
tate, chelating, macrocyclic, or cryptand) can be viewed as a
In general, the larger the number of donor atoms, the greater the increase in stability metal-binding domain that can be combined with any other
with the reservation that complexes with the same geometry can be obtained. domain to give a new bespoke conjugate ligand. The imple-
a
Water molecules are omitted from the equations for clarity. mentation of the concept is only limited by the imagination
and requirements of the synthetic chemist. In Figure 1, a
selection of commonly encountered metal-binding domains
Table 4 Quantitative aspects of the macrocyclic effect11
is presented. A good overview of metal-binding domains in
Reactiona lg K D supramolecular chemistry has recently been published.13
A typical example of the toolkit in action is seen in L8, a
Cu2þ(aq) þ L2 ¼ [Cu(L2)]2þ(aq) 23.2 ligand which was designed to act as a tridentate to one metal
Cu2þ(aq) þ L3 ¼ [Cu(L3)]2þ(aq) 26.5 3.3 center and a bidentate to a second and at the same time to
a
Water molecules are omitted from the equations for clarity.
allow maximum electronic communication between the two
(Scheme 1).14,15 In this case, the bpy end may be addressed by
a {Ru(bpy)2} moiety and the tpy end by {Ru(tpy)} to give the
dinuclear complex [(bpy)2Ru(L8)Ru(tpy)]4þ.
Table 5 Comparison of the stability of Kþ complexes of macrocyclic
and cryptand ligands11

Liganda lg K D 8.01.3 The Synthetic Toolkit: Favored Conjugation

Reactions
L6 6.1
L7 10.8 4.7 [Link] The Synthetic Organic Chemistry
a
MeOH at 298 K
The purpose of this section is to briefly introduce some of the
synthetic routes that have proved to be particularly popular in
conjugating metal-binding domains. In particular, the empha-
sis is on the applicability and the limitations of the methods.

[Link].1 The Suzuki reaction

NH N The Suzuki reaction involves the formation of CdC bonds by the
NH2 H2N NH HN
cross-coupling of an aryl, alkyl, or vinyl boronic acid, borate ester,
N HN or borane with an aryl or vinyl halide or triflate using a variety of
palladium catalysts (Scheme 2).16–18 The boronic acids are often
NH HN NH HN
commercially available or are readily prepared through standard
functional group interconversions. The reaction is extremely tol-
H2L1 L2 L3 erant to a wide variety of functional groups such as carboxylic
acids, esters, alcohols, aldehydes, and ketones and this is one of
The concept of ‘hole-size,’ the crown ether internal van der the reasons for its popularity in natural product synthesis. An
Waals diameter, allows one to design macrocycles which are likely example of the synthesis of a simple 2,20 -bipyridine derivative19
to be optimized for the binding of a particular metal. The ‘hole- is also presented in Scheme 2.
size’ concept makes assumptions about the conformation of the The advantages of the Suzuki reaction are multifold: The
ligand and the coordination number of the metal and must be tolerance to functional groups, the wide range of catalysts with
used with caution,12 but is nevertheless useful in designing crown various selectivities, the regio- and stereospecificity, the solvent
ether ligands optimized for alkali metal ions (L4 for Liþ, L5 for tolerance, and the ability to perform the reaction under a wide
Naþ, L6 for Kþ, etc.). variety of conditions. There are, however, some limitations to
Just as we can conceptually derive L3 from L4 by ‘closing the the reaction in terms of ligand synthesis. The first is that the
loop,’ so we can extend the concept to ligands which product of the desired reaction is, by definition, a ligand and
4 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

Monodentate

OR O– NR2 S- SR PR2 AsR2

R
R R OH
C N R
N N
N S R R

Bidentate
O-
R2N NR2 O-
N N N N O
O

O
R2P PR2 R2P PR2
H2N O-

Tridentate
R
N
N NR
N R N
NR 2 NR 2
N N R

Tetradentate

NR RN NH N
NH N

NR2 R2N N HN
N HN

Porphyrin Phthalocyanine
Figure 1 Typical metal-binding domains which can be combined into conjugate ligands. In all cases, R can be a hydrogen or an organic group.

Target 1 MBD 1 MBD 2 Target 2

N N
N N
N
Ru N N Ru
N N N
N N

N N

N N

L8
8
Scheme 1 Ligand L : this ligand design presents both bidentate and tridentate metal-binding domains.
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 5

can deactivate the catalyst by coordinating to the palladium. sensitive to oxygen or water.26,27 The most common type of
Competing dehalogenation reactions can, on occasion, prove click chemistry is the copper-catalyzed Huisgen 1,3-dipolar
to be troublesome. Finally, there are combinations of reactants cycloaddition of alkynes to azides to yield 1,4-disubstituted-
which refuse to give good yields in the Suzuki reaction under a 1,2,3-triazoles (Scheme 5).28 An example (Scheme 5)29 is the
variety of conditions. application to the preparation of 1,2,3-triazolylpyridines for
the preparation of complexes to be used as dyes in dye-
[Link].2 The Stille reaction sensitized solar cells. The methodology has been extended to
The Stille reaction is complementary to, and rather similar to, the conducting click chemistry directly on coordinated azides30
Suzuki reaction but utilizes organotin reagents in place of the and coordinated alkynes.31,32
boron derivatives (Scheme 3).20–22 The order of transfer of groups
from the tin in the reaction is alkynyl > alkenyl > aryl > allyl ¼ [Link].5 Schiff base chemistry
benzyl > alkyl, which leads to the common use of SnMe3, SnEt3,
In contrast to the ‘new’ methodologies discussed above, the
or Snn Bu3 as the scaffold for the transfer of other groups. The
‘old favorites’ are still widely used. One of the most commonly
reaction is rather more oxygen sensitive than the Suzuki reaction used reactions is still the condensation of a primary amine with
and must usually be conducted under an inert atmosphere. An
an aldehyde or ketone to generate an imine (Schiff base)33,34
example of the use of the Stille reaction for the synthesis of
or the intermediate aminol (Scheme 6).35 This strategy has a
2,20 :60 ,200 -terpyridines is also presented in Scheme 3.23
number of attractions: First, the imines are good p-acceptors
and complexes with electron-rich transition metals are stabi-
[Link].3 Sonogashira coupling lized by synergic backbonding and, second, the imines, which
The Sonogashira palladium-catalyzed cross-coupling reaction are often hydrolytically unstable, may be reduced (in situ or
between (usually) a halide attached to an sp2 carbon atom and after isolation) to secondary amines (Scheme 7). A typical
a terminal alkyne is well established,24 and the methodology recent example of the use of a Schiff base condensation for
(top of Scheme 4) is an excellent means of coupling vinyl the preparation of a dinucleating salen-related ligand is also
halides, aryl iodides, aryl bromides, or aryl triflates with termi- shown in Scheme 6.36,37 Scheme 7 includes a recent example
nal alkynes. The example shown in Scheme 425 illustrates two of the conversion of helicating Schiff base ligand to a reduced
successive Sonogashira couplings and the need, in this case, for secondary amine.38 The design of chiral Schiff base ligands
protection of one end of the initial alkyne during the first step plays an important role, for example, in stereoselective organic
of the synthesis. transformations39 and asymmetric catalysis.40,41

[Link].4 Click chemistry [Link].6 Grubbs’ catalyzed ring-closing metathesis

A powerful new type of reaction that is beginning to be used in Grubbs’ catalyzed ring-closing metathesis (RCM, Scheme 8) is
the conjugation of metal-binding domains and functional an effective strategy for the synthesis of large macrocycles and
groups is called click chemistry. Sharpless defined a click reac- works under very mild reaction conditions.42,43 Sauvage was the
tion as one that is generally applicable and requires no special first to combine a tetrahedral {Cu(phen)2}þ domain with
apparatus, uses readily available and cheap reagents, and is not Grubbs’ RCM to template the formation of a catenane44–46; the

[Pd]
ArBr + RBX2 Ar–R

O [Pd(PPh3)4], CuI, K2CO3

N B THF, Δ, 24 h
O N
Ph Br N CHO N N
CHO
70%
Scheme 2 The Suzuki cross-coupling reaction and an example of its application to the synthesis of 2,20 -bipyridine-6-carbaldehyde. The unusual boron
derivative is selected to overcome the instability of the pyridine-2-boronic acids.

[Pd]
ArBr + RSnR⬘3 Ar–R
CO2Et
CO2Et
[Pd(PPh 3) 4]
+ 2 N
toluene
Cl N Cl N SnnBu3 N N

85%
Scheme 3 The Stille cross-coupling reaction and an example of its application to the preparation of 2,20 :60 ,200 -terpyridines.
6 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

[Pd], CuI, Et3N

R H + X R

H
Br 1. [Pd], CuI, Et3N
+2H
OH 2. Deprotection
Br
H

[Pd], CuI, Et3N

N OTf

N
N N
N N

N
N

Scheme 4 Application of the Sonogashira palladium-catalyzed cross-coupling reaction in ligand synthesis.25

R1
Cu(I) N
R1 + R2N3 N
N
R2
N

N N
N
N3 N TMS
[Cu(CH3CN)4][PF6] [Cu(CH3CN)4][PF6]
N
N
Cu, DIPEA N KF, Cu, DIPEA
N N N3

R
R
R
R
Scheme 5 The copper-catalyzed Huisgen 1,3-dipolar cycloaddition click chemistry and an example of application to the preparation of 1,2,3-triazolyl-
pyridine ligands.

pioneering example is shown in Scheme 8.44 Following from uninvestigated and the desired complexes are obtained with-
this ingenious strategy, a variety of ring-closing steps has resulted out additional detailed investigations. Although historically
in the assembly of catenanes, knots, and rotaxanes.47–55 template reactions were common in the preparation of com-
plexes with macrocyclic ligands,58–60 they are also the key to
the preparation of topologically complex systems61 as well as
being increasingly used for the preparation of ‘simple’ com-
[Link] Template Reactions
plexes. The role of the templating metal ion can be evidenced
One additional strategy that has been widely used for ligand by the isolation of ‘intermediate’ complexes, formed prior
synthesis is the so-called template approach in which organic to the metal-free ligand. An example is the condensation
components are reacted together in the presence of metal ions of 1,6-bis(30 -hydroxy-40 -formylphenyloxy)hexane and 1,2-
to generate metal complexes of the desired ligands directly.56,57 In diaminobenzene in the presence of Ba2þ followed by
many cases, these reactions are mechanistically obscure or removal of the latter by treatment with Na2SO4.62
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 7

R1 R1 R1
+ OH NR
R NH2 O
R2 R2 NHR R2

tBu
tBu
R R
tBu
R
O R2
OH
OH M O
N N
CHO
NH2 N
R1
NH2 M(OAc)2
NH2

R1 R2 R1
H2N N
N OH M N
O
H2N CHO R2
HO O
NH2
tBu tBu
R R

Scheme 6 The reversible condensation of a primary amine and a carbonyl compound to give an aminol or an imine. The stepwise synthesis of a
multinucleating ligand through repeated Schiff base condensation is presented as a recent example of this approach.

R1 [H] R1
NR H NHR
R2 R2

H2N NH2
H H
O O N N NH HN
Na[BH4]
N N N N N N

N N N N N N

Scheme 7 The reduction in a Schiff base leads to a hydrolytically stable secondary amine. The dinucleating ligand shown forms dinuclear helicates.

axial sites free for additional donor and/or reversible binding of

8.01.4 Ligand Design for Macrocycles small molecules (e.g., O2 in the case of hemoglobin).
Template synthesis (see Section [Link]) of macrocyclic
Macrocyclic ligands with N-donors63 include porphyrins ligands (e.g., azacyclams)74 is a common strategy, and is exem-
(Figure 1 shows the parent compound)64 which are ubiquitous plified in Scheme 9 using nickel(II) which, having a d8 elec-
in nature, for example in myoglobin, hemoglobin, and cyto- tronic configuration, shows a preference for square-planar
chrome P-450. Crown ethers (see Section [Link]) offer a set coordination. Thus, in the first step of each reaction in
of hard O-donors to a metal ion and the hydrogen-bonding Scheme 9,75,76 the Ni2þ ion controls the spatial position of
potential of the oxygen sites permits these macrocycles to also the donor atoms in the acyclic ligand. The intermediate coor-
function as hosts for stabilizing a range of oxonium ([(H3O) dinated ligand is now preorganized for ring closure. In
(H2O)n]þ) ions.65 Softening the donor sets leads to macrocycles Scheme 9, the cyclization step is nucleophilic substitution in
incorporating P- and As-donors,66–68 or S-,69–71 Se-, and Te- the first reaction, and a Schiff base condensation in the second.
donors.70–73 If the coordination geometry of the metal ion coor- So-called compartmental macrocyclic ligands77–80 are, as
dinated within a macrocyclic ligand is to control the assembly, the name suggests, ligands that possess two or more
the backbone of the ligand must be sufficiently flexible to allow ‘compartments’ that are designed to accommodate two or
the required conformational change. By contrast, the metal- more metal ions to generate either homo- or heterometallic
binding domain in a ligand such as a porphyrin is rigid and complexes. The Schiff base methodology34,81,82 is popular for
dictates a planar (or near-planar) coordination geometry, leaving the synthesis of ligands of the type shown in Scheme 10; the
8 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

Grubbs¢ catalyst

X -C2H4 X

N Grubbs¢ N
N catalyst N
Cu+ Cu+
N N
N N

O O O

N
Each initial acyclic ligand =
N

O
O O
Scheme 8 Schematic representation (top equation) of ring-closing metathesis (RCM) catalyzed by one of the family of Grubbs’ catalysts, and an
example of catenane formation using Cuþ to direct the RCM reaction.

CH2Br 2+
SH
N N S CH2Br N S
Ni2+
Ni Ni
-2Br-
N N S N S
SH

2+ 2+
O

H HN NH
Ni2+ HN NH2 O
N NH2 Ni
H2N N Ni
H NH2 HN NH
HN

Scheme 9 Use of nickel(II) to template the synthesis of N2S2 and tetraaza-macrocyclic ligands.

R
R1 R2

O OH O R1 R2

NH2 H2N N OH N
X and Y = spacers e.g. (CH2)x
X Y X Y
H2N (CH2)xNH(CH2)x
NH2 N OH N

O OH O R4 R3

R4 R3
R

R
Scheme 10 General form of a compartmental ligand, H2L, derived from condensation of various amines with derivatives of 2,6-diformylphenol. The
macrocyclic ligand has two N,O,N’-metal-binding pockets, the proximity of which depends on X and Y.
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 9

+
O

OH
N N N
O
LnX3 Ln
+ 2 Cl O HO Cl
2 Cl OH
H2N N NH2
O N N N

HO
d-block MX2 f-block LnX3

d,f-heterodimetallic f,f-homo- or
complexes heterodimetallic
complexes
Scheme 11 Schiff base compartmental ligand assembly in the assembly of d,f- and f,f-heterodimetallic and f,f-homodimetallic complexes. Basic
conditions are required for phenol deprotonation.

conjugate base L2– of the ligand H2L illustrated in Scheme 10

possesses two N,O,N’-metal-binding pockets, the proximity of
which can be altered by choosing appropriate X and Y spacers. O N N
Symmetrical spacers (X ¼ Y) are more common than asymmet- NH2 OH MeCN OH HO
rical ones, and the spatial properties of the macrocyclic cavity +
depend upon the amines chosen for condensation with NH2 OH OH HO
2,6-diformylphenol.83 Varying the substituents R1  R4 permits O
N N
HO OH
the design of compartmental macrocycles having two different N N
metal-binding domains. The ability of a given ligand to recog-
nize two different metal ions and hold them in close proximity
provides a pathway to tune the properties of a heterodimetallic Scheme 12 Nontemplated synthesis of a [3 þ 3] macrocyclic ligand.
system, for example, by exchanging the metal ions, through
redox processes, etc. One of the interests in the design of As mentioned above, imine bond formation during Schiff
compartmental ligands is as models for the active sites of base condensation reactions is reversible90 and this may lead to
metalloenzymes, for example, the dicopper-containing hemo- mixtures of macrocycles of different sizes. In a template reac-
cyanin and diiron-containing hemerythrin.84 tion, the reversibility of the imine bond formation is advanta-
Compartmental ligands can be designed to accommodate geous in that it permits for correction of ‘errors’ in the assembly
both d- and f-block metal ions.85 An example is shown in process, that is, if there is a mismatch in metal coordination
Scheme 11; in this case, an initial templated Schiff base con- preferences and ligand ring size, the latter can contract or
densation gives a mononuclear f-block metal complex which expand through breaking and reforming the imine links (see
reacts further to give either a homo- or a heterodinuclear below). The incorporation of chiral domains into macrocyclic
complex. Dimetallic complexes can also be achieved by com- ligands is readily achieved using the Schiff base approach and
bining aldehyde, amine, and the two metal salts in one pot.86 the pool of chiral diamines gives ready access to a variety of
A symmetrical macrocyclic ligand of the type shown in enantiomerically pure Schiff base macrocycles81 with a range
Scheme 10 in which X ¼ Y, R1 ¼ R4 and R2 ¼ R3 is referred to of applications. A recent example91 also highlights potential
as a [2 þ 2] macrocycle. Less common are [3 þ 3] or higher difficulties arising from reversible imine bond formation. Reac-
macrocyclic ligands.87 The condensation reaction shown in tion of 2,6-diformyl-4-substituted phenols with D-(þ) or D,L-
Scheme 12 generates a [3 þ 3] macrocycle, and this is particu- 1,2,2-trimethylcyclopentane-1,3-diamine in the presence of
larly noteworthy because a yield of 91% is achieved without Naþ as the templating metal ion results in the formation of
the need for a templating metal ion.88 A likely driving force for predominantly [3 þ 3] Schiff base macrocyclic ligands (both
the latter is the low solubility of the product which results in its enantiopure and racemates). However, once treated with Cd2þ,
removal from the reaction mixture, preventing reversible open- Zn2þ, Ni2þ, Mn2þ, or Cu2þ ions, ring contraction occurs as a
ing of the imine bonds. This family of ligands has been devel- result of C]N bond cleavage and reformation. The driving
oped using template metal ions as shown in Scheme 13. force for the latter appears to be the geometrical preferences
Selectivity of the different metal ions for dissimilar binding of the metal ions.
domains (four- vs. six-coordinate) is key to this assembly Macrocycles with donor atoms from groups 15 and 16 are
process.89 Large macrocyclic ligands of the types shown in extremely well documented, but a less well-recognized class of
Schemes 12 and 13 offer a pocket of hard O-donor atoms macrocyclic ligands consists of those containing N-heterocyclic
within a moderately flexible environment. This encourages carbenes as the donor groups.92 Two synthetic strategies are
the assembly of clusters of, for example, zinc(II) ions.87 usually followed. The first involves coordination of
10 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

3+ O O 3+
O O NH2
O O N N
2+
Zn Zn
OH Zn
La3+ O O O NH2
O O
OH O La O O La O
O Zn O N N
O Zn Zn Zn
O O O O
O O
O O N N
O O

Scheme 13 Mixed-metal ion-templated synthesis of a [3 þ 3] macrocyclic ligand.

2+
PMe3
4 + Me P Pt PMe3
3

N N3 PMe3
C

2+ 2+

N N
HN NH N N
H H
N N DMF, Cl2CO N N
Pt Pt
N N -4H2O N N
H H
HN NH N N
N N

Scheme 14 Example of templated formation of a macrocyclic ligand containing N-heterocyclic carbene donors.

functionalized N-heterocyclic carbenes to a templating metal ion O

followed by cyclization. In Scheme 14, the square-planar plati- O O O O O
num(II) center positions the monodentate carbene ligands so as O O O O
to direct cyclization in the second step.93 The second synthetic O O
O Cs+ O
method is the preparation of a macrocyclic polyazolium ion O O Cs+ O O
O
O O O
followed by deprotonation.
O O
Combining two or more macrocyclic ligands into a single
array provides the basis for systems for sensing applications. A S
Au S
pertinent example comes from the work of Yam and S
Au
coworkers94 and involves reversible group 1 metal-ion binding Au S Au
by pendant crown ether ligands, which induces reversible
switching on/off of aurophilic interactions and concomitant Scheme 15 Using reversible cesium ion capture between a pair of
photophysical changes (Scheme 15). The combination of crown ether ligands to switch Au  Au interactions on and off.
reversible host–guest interactions with changes in electronic
spectroscopic properties is a powerful means of developing
sensing devices.95 The coupling of azamacrocyclic ligands has metal nodes. Thus, ligand design alone cannot be used as a
been reviewed in depth96 and allows access to arrays that have means of directing an assembly. Rather, it works synergistically
applications in biomedical imaging and catalysis. with the geometrical preferences of the metal node, and
together, these direct the construction of one-dimensional
chains, two-dimensional sheets, or three-dimensional
8.01.5 Ligand Design for Coordination Polymers networks.97–101 In this chapter, it is impossible to give a com-
and Networks prehensive account of all ligand types that are used in coordi-
nation polymers and networks. We therefore restrict this
The assembly of coordination polymers and networks critically account to popular ligand types such as pyridine- and
depends upon the compatibility of the donor properties of carboxylate-based ligands, noting that the general principles
ligands coupled with the coordination preferences of the outlined below can be applied to other families of ligands.
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 11

In 1992, Constable introduced the idea of using polytopic tpy- of the latter differ: That radiating from a tetrahedral carbon
based (tpy¼ 2,20 :60 ,200 -terpyridine) ligands as building blocks for atom is designed to act as a node in a three-dimensional
the assembly of coordination polymers and oligomers.102 A pre- coordination network, while that centered on a porphyrin or
requisite for the design of ligands for one-dimensional coordina- 1,2,4,5-substituted benzene unit is a node for a two-
tion polymers is the presence of two donor atoms that are dimensional sheet. Similar palettes to Scheme 17 can be con-
mutually sterically unhindered. Using bipyridine as an example, structed for the other metal-binding domains. For example,
Scheme 16 illustrates that 4,40 -bipyridine is ideally suited for starting from a carboxylate ligand ðRCO2  Þ, one can generate
polymer formation, while 2,20 -bipyridine favors chelation. ligand nodes based on oxalate ligands (O2CCO2 ) and
Although binding two metal domains by 2,40 -bipyridine may polycarboxylate ligands. Combining pyridine and carboxylate
be sterically disfavored, it is not precluded.103 Coordination poly- metal-binding domains, bridging species such as isonicotinate
mers featuring 4,40 -bipyridine are extremely well established. (conjugate base of isonicotinic acid or 4-pyridylcarboxylic
However, despite the fact that the 2,30 -, 3,30 -, and 3,40 -isomers acid) are obtained with different metal selectivities at the N-
of bpy exhibit suitably directional donor atoms (Scheme 12), and O,O0 -donor ends.
coordination polymers involving 3,30 - and 3,40 -bipyridine are Since the early work of Constable and Cargill
poorly represented in the Cambridge Structural Database,104 Thompson,102 ditopic tpy-ligands have played an important
and 2,30 -bipyridine has received negligible attention as a building role in the development of one-dimensional coordination
block.103 polymers. Rod-like, high-molecular-weight polymers contain-
If one is using the ligand to dictate an infinite assembly, ing rigidly connected {Ru(tpy)2} domains were reported by
then progression from a one-dimensional chain to a two- or Rehahn and coworkers in 1999.106,107 The kinetically inert
three-dimensional network requires the ligand designer to ruthenium(II) center (low-spin d6) is critical, and the contrast-
(1) Introduce further metal-binding domains and (2) link ing behavior of systems containing labile metal(II) ions (e.g.,
these domains such that the building block exhibits a suitable iron(II) and cobalt(II)) has been highlighted.108,109 The
spatial pattern. Using pyridine as an example, Scheme 17 illus- dynamic nature of the polymeric systems means that charac-
trates the relationships between selected ligand nodes (i.e., the terization of the systems is nontrivial.110,111 One-dimensional
ligand building blocks) that are suited for one-dimensional coordination polymers constructed from {M(tpy)2} units and
chains, two-dimensional sheets, and three-dimensional net- ditopic tpy–X–tpy ligands (X ¼ spacer) attract considerable
works. The use of diazines (e.g., pyrimidine or pyrazine) or interest because of the application of their photophysical and
triazines in place of pyridine gives prototype bridging ligands electrochemical properties in materials science.112 Over the
that, upon metal coordination, facilitate the formation of past decade, there have been significant advances in the devel-
sheets, while tetrazolyls have been shown to be effective opment of polymers in this family that exhibit luminescent,
ligands in directing the assembly of two-dimensional sheets electroluminescent, electrochromic, magnetic, and related
and diamondoid networks.105 In terms of assembling one- properties.113–121 While coordination polymers incorporating
dimensional chains, pyridine metal-binding domains can be the tpy metal-binding domain are particularly well explored
linked by flexible spacers (exemplified by alkyl units) or rigid and continue to be the focus of attention, analogous donor sets
spacers (exemplified by arene units) giving control over the are provided by a family of related ligands based upon ditopic
properties and dimensionality of the final coordination poly- 2,6-bis(10 -methylbenzimidazolyl)pyridine ligands. Significant
mer. Altering the number of spacer units (e. g., (CH2)n) con- progress has recently been made in the development of metal-
trols the distance between metal centers in the coordination lopolymers utilizing these ligands.122–126
polymer. Additional variation can be achieved by choice of Designing ligands for coordination polymers has to take
isomer, for example, different isomers of bipyridine as illus- into account that not all donors may bind a metal ion. A
trated in Scheme 16, or different isomers of the arene spacer. pertinent example again comes from polypyridine chemistry.
The lower part of Scheme 17 shows the connection of 4- 4,20 :60 ,400 -Terpyridine (4,20 :60 ,400 -tpy, Scheme 18) is one of 48
pyridyl metal-binding domains to give new ligands which possible isomers of terpyridine and while the outer two pyri-
will bridge three or four metal nodes. Moreover, the examples dine nitrogen atoms in 4,20 :60 ,400 -tpy bind metal ions, the

M N N M N M
N N N
M M
4,4⬘-bpy 2,2⬘-bpy 2,4⬘-bpy

M M
M
N N
N
N N N M

M M
2,3⬘-bpy 3,3⬘-bpy 3,4⬘-bpy
Scheme 16 Directional properties of the donor atoms in isomers of bipyridine (bpy).
12 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

n n
N
N N N N

N N N N N

Introducing
more donor Linking units in one dimension
atoms to the
ring
N

Pendant units for two or three dimensions

N N N

NH N
N N
N N
N HN

N N
N
N
N

N N N

Scheme 17 Strategies for the development of multinucleating ligands for use in coordination polymers based on pyridine metal-binding domains.

120⬚
Mn+ Mn+
N N N N
N N
120⬚
Mn+ Mn+
4,2⬘:6⬘,4⬙-terpyridine
3,2⬘:6⬘,3⬙-terpyridine (trans,trans)

Mn+
N N N

N N N

Mn+ Mn+ Mn+

3,2⬘:6⬘,3⬙-terpyridine (cis,trans) 3,2⬘:6⬘,3⬙-terpyridine (cis,cis)

Scheme 18 Divergent binding mode of 4,20 :60 ,400 tpy compared with possible binding modes of 3,20 :60 ,300 -tpy. The trans,trans. . . . labels refer to the
relative conformations of pairs of adjacent pyridine rings in the 3,20 :60 ,300 -tpy ligand.

central one typically does not. This results in 4,20 :60 ,400 -tpy and (e.g., X ¼ OAc, Cl, I)127–132 or linear {Zn2(m  OAc)4N2}131,133
its derivatives being suited to the assembly of one-dimensional metal nodes. Note that both of these are topologically equiva-
coordination polymers; in combination with, for example, lent. Subtle changes in the spatial properties of a coordination
zinc(II), the choice of anion leads to bent {ZnN2X2} polymer can be achieved by modifying the vectorial properties
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 13

of the ligand. A relevant example is the consequence of going typically followed. The first usually uses ‘rigid-rod’ ligand linkers
from 4,20 :60 ,400 -tpy to 3,20 :60 ,300 tpy while maintaining a com- with the metal nodes defining the internal angle, and hence the
mon metal node: 4,20 :60 ,400 -tpy and 3,20 :60 ,300 -tpy both exhibit size, of the polygon. A prototypical example is the use of {LPtII}
an N,N’-mode but, unlike 4,20 :60 ,400 -tpy, the 3,20 :60 ,300 -isomer units as a molecular corner where L is a chelating ligand (e.g., 1,2-
can adopt various conformations (Scheme 18) resulting in a diaminoethane, en) with bite angle around 90 . The use of
change from planar to undulating zigzag coordination poly- platinum(II) (d8) ensures a square-planar metal center, and
mer chains in the solid state.134 incorporating the chelating ligand L restricts the coordination
At first glance, the groups of ligands at the top right of environment for incoming ligands to cis. The consequence of
Scheme 17 may appear ideal only as building blocks in one- these two limitations is that when combined with a ‘rigid-rod’
dimensional coordination polymers, but of course the out- ligand, {LPtII} ‘corner’ domains direct the assembly of a molec-
come of the assembly process also depends upon the metal ular square. Scheme 20 shows a classical example from the work
node. A ligand such as 4,40 -bpy is a ‘rigid-rod’ building block of Stang and coworkers.142
and combination with a linear (or topologically equivalent) The size of a molecular polygon can be adjusted by judicial
metal node can only lead to a one-dimensional assembly choice of ligand and metal. The P,N,N’,P’-ligand shown in
(Scheme 19). However, combined with a metal node of Scheme 21 can act as a bis(P,N-chelate) or simply as a P,P’-
some higher connectivity, for example, tetrahedral, square pla- donor. The key is the relative strengths of the metal–P and
nar (Scheme 19), or octahedral, 4,40 -bpy can function as a metaldN bonds. The molecular square shown on the left of
building block in two- or three-dimensional networks. Note Scheme 21 contains five-membered RhNCCP-chelate rings
that the metal ion may also bind additional ligands such as Cl–, (Rh(I) is d8 and square planar). Reactions with small donor
RCO2  , etc. which are ignored when considering the connec- molecules or ions such as CO, MeCN, and Cl– result in addi-
tivity of the metal node in the polymer.135 tion of the latter with concomitant cleavage of the RhdN
Given enough flexibility in the ligand backbone, a one- bonds but retention of the stronger RhdP bonds. The overall
dimensional coordination polymer may exhibit a twisting of result is an expansion of the molecular square (Scheme 21).143
the ligand–metal framework about the direction of propaga- The ‘directional bonding approach’144 described above is
tion. If the ligand itself is achiral, the result may be a racemic now a mature area of molecular engineering. Starting from a
crystal with equal numbers of left-handed (P) and right- molecular toolbox of ‘rigid-rod’ ligands and metal ‘corners’
handed (M) helices. There is significant interest in this with different geometrical preferences, it is possible to direct
area,136,137 particularly with ligands being designed so that the formation of metallopolygons ranging from triangles to
homochiral packing is favored and enantiopure single crystals hexagons. Of course, in a matrix of possibilities, the ligand
are achieved. By using chiral ligands, good stereocontrol may (rather than the metal) can be used to define the internal
be attained and with the isolation of homochiral crystals.138 angle of the polygon. This leads to the second strategy for
constructing metallopolygons which relies upon the vectorial
properties of the ligand to define the internal angle of the
8.01.6 Ligand Design for Metallopolygons polygon and hence it is the design of the ligand that is critical.
The work of Newkome and coworkers elegantly exemplifies
In contrast to the coordination polymers described above, a this approach to the construction of metallopolygons and
metallopolygon is defined here as a discrete multinuclear, cyclic, relies upon the use of octahedral {M(tpy)2} domains linked
coordination complex. To achieve such an assembly,139–141 by intraligand spacers that predetermine the size of the molec-
complementarity between ligand and metal building blocks is ular assembly. An example is shown in Scheme 22145; the
crucial and potential sites for extension of the assembly must be {Ru(tpy)2} units are effectively linear linkers, and choice of
blocked. Two strategies for the assembly of metallopolygons are a 1,3-substitution pattern at the arene linker X in the ditopic

M M M

M M M

M M M M M

M M

= N N

Scheme 19 For a ‘rigid-rod’ ligand such as 4,40 -bpy, the final outcome of an assembly process depends upon the coordination preferences of the
metal node. This is illustrated here by two- and four-coordinated metal centers.
14 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

Ph2 From the toolbox:

P OTf
Pt + N N
P OTf
Ph2

CH2Cl2, room temp.

PPh2 Ph2P
Ph2P Pt N N Pt PPh2
Self-assembly
N N

N N

Ph2P Pt N N Pt PPh2
PPh2 Ph2P

Scheme 20 Designing building blocks for molecular squares. Schematic representation: ligand, red; metal node, blue.

N
Ph2P
PPh2
N

Ph2 Ph2
OC P N N P CO
4+ Rh Rh
Ph2P PPh2 Ph2P Cl Cl PPh2
Ph2P Rh N N Rh PPh2
N N
N N

N N
N N

Ph2P Rh N N Rh PPh2 Ph2P Cl Cl PPh2

Ph2P PPh2 Rh Rh
OC P N N P CO
Ph2 Ph2

Scheme 21 Managing the size of a molecular polygon by ligand control.

tpy–X–tpy ligand ensures the 120 internal angle required to described.149 Despite these ligands being rigid and predesigned
direct the assembly of the metallohexagon.146 The use of the for the formation of metallohexacycles, the reactions shown in
same color coding in the cartoon representations in Scheme 23 lead to mixtures of metallopentacycles and/or
Schemes 20 and 22 emphasizes the roles of the metal or ligand metalloheptacycles (minor products) and metallohexacycles
in controlling the assembly process. Use of 1,3,5-tris{40 - (major products).150,151 Solution nuclear magnetic resonance
(2,20 :60 :200 -terpyridinyl)}benzene in conjunction with the 1,3- (NMR) spectroscopic studies indicate that there is no equilib-
bis{40 -(2,20 :60 :200 -terpyridinyl)}benzene derivative shown in rium between the species, despite iron(II) being kinetically
Scheme 22 directs the coupling of six of the metallohexagons labile.150 Larger metallomacrocycles can be favored by incor-
to a honeycomb-like assembly.147 1,3-Bis{40 -(2,20 :60 : porating a kinetically inert metal center such as ruthenium(II)
2“terpyridinyl)}benzene reacts with Cd(NO3)2  4H2O to into the predesigned 120 ligand building block and then
give a [6 þ 6] metallomacrocycle analogous to that shown in reacting these metalloligands with, for example, iron(II).151
Scheme 22,148 and a related zinc(II) hexacycle has also been We return to the concept of metalloligands in Section 8.01.9.
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 15

From the toolbox:

N N
N N
Cl3Ru RuCl3
N N

[Cl3Ru(L)RuCl3]

L
N-ethylmorpholine, MeOH

Self-assembly
N N
N N N N
Ru Ru
N N N N
N N

N N
N N N N
Ru Ru
N N N N
N N

N N
N N N N
Ru Ru
N N N N
N N

Scheme 22 Designing building blocks for molecular hexagons. Schematic representation: ligand, red; metal node, blue.

Asymmetrical metallohexacycles can be assembled using the Other ligands that retain a 60 internal angle but have less steric
principles detailed above but combining mixed ligands, each crowding of the metal-binding domains are L9 and L10.155
with a designed 120 angle subtended within the ligand.152 The molecular square illustrated in Scheme 20 is favored
Arene-centered ditopic ligands such as those illustrated in because the platinum(II) precursor contains labile triflate ligands,
Schemes 22 and 23 can readily be redesigned to provide and a nonlabile chelating ligand. Thus, only two sites on the
tritopic building blocks. Whereas such ligands may be suited metal ion are free for interaction with 4,40 -bipyridine. A more
to the assembly of coordination networks, it is possible to drive complex situation arises if all the ligands on the metal center are
the process toward discrete systems by stepwise assembly labile. Palladium(II), like its heavier group 10 congener, invari-
involving in the initial step a kinetically inert metal ion ably forms square-planar complexes, but the lability of PddN
bound to a stoppering unit (Scheme 24). The final product bonds is greater than that of PtdN bonds. Reaction between [Pd
in Scheme 24 possesses six iron(II) centers within the metallo- (en)(OTf)2] or [Pd(en)(ONO2)2], the 4,40 -bipyridinium-based
hexacycle and six ruthenium(II) ions bound in exocyclic ligand shown in Scheme 25, and [Pd(NCMe)4]2þ (in which all
domains.153 This assembly contrasts with organic macrocyclic ligands are labile) leads to the formation of a combinatorial
ligands designed to specifically bind exocyclic metal ions.154 library of products in solution. The size of each metallopolygon
Ligand design for metallohexagons requires the ligand to is fixed by the angular dependence of the ligand and the acceptor
exhibit two metal-binding domains directed at 120 with respect properties of the {Pd(en)}2þ ‘corner’. Structural variation is a
to one another. As the examples above show, a 1,3-substitution consequence of the number of [Pd(NCMe)4]2þ ions with which
pattern on a central arene ring is an ideal strategy to achieve such the ligand interacts.156
an objective. In contrast, a 1,2-substitution pattern in the arene So far, this section has focused upon metallopolygons in
core results in a 60 internal angle and a building block suited to which the metal atoms are (or are approximately) coplanar. A
the assembly of a metallotriangle. 1,2-Bis(2,20 :60 ,200 terpyridin-4- range of ditopic ligands bind metals so as to produce helical or
ylethynyl)benzene, L (see Scheme 4), is a ligand designed for interwoven metallocycles (Scheme 26, top) and this area of
this purpose. It reacts with FeCl2  4H2O or RuCl2(DMSO)4 to ligand design and supramolecular assembly was reviewed in
give the metallotriangles [Fe3L3]6þ or [Ru3L3]6þ, respectively.25 2000 by Swiegers and Malefeste.157 A more recent example
16 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

N
N
N
N
N
N

60⬚ 60⬚

N
N
N
N
N

N
9
L L10

involves the design of a ditopic ligand possessing both phen unit combines with 2,4,6-tris(4-pyridyl)-1,3,5-triazine to give
(phen ¼ 1,10-phenanthroline) and tpy domains (Scheme 26, an octahedral Pd6L4 cage in the four ligands that lie over
bottom). The ligand is prepared using Suzuki methodology alternate faces of the cage (Scheme 29). The three pyridine
and reacts with Cu(OAc)2 to selectively give a metallohexacycle donors in the ligand are fixed at 120 with respect to one
containing {Cu(phen)(tpy)} units. In this case, the preference another. This coupled with the constraints of the cis - {(en)
for the latter over {Cu(phen)2} or {Cu(tpy)2} directs the reac- PdII} unit ensures a directed assembly process. These design
tion to the desired product.158 Helical metallocycles must be principles have been elaborated using a palette of related
distinguished from their planar analogs in which metal-binding ligands to produce a range of molecular architectures.165
domains in a ditopic (or higher) ligand are engineered to bind Stang and coworkers have summarized the construction of
two (or more) metal ions on the same side of the ligand, forming three-dimensional structures such as that in Scheme 29 in
what are referred to as coordination ‘grids.’157,159–162 Polypyridyl terms of the combination of tritopic (the ligands) and ditopic
ligands with two or more bidentate metal-binding domains are a (the metal corners) subunits, and an in-depth review in 2011
popular choice for grid assembly and an example of a [22] details a wide range of examples.144 The area is given further
grid163 is shown in Scheme 27. coverage in Chapter 8.02 (by Fujita) in this work.
Even though 4,20 :60 ,400 -tpy is designed for the formation of
coordination polymers (see above), discrete metallohexagons
are also formed in reactions of derivatives of 4,20 :60 ,400 -tpy and
ZnCl2. Zinc(II) exhibits a tetrahedral coordination sphere, mean-
8.01.8 Metalloligand Design
ing that the angle subtended at the metal center is not the ideal
A metalloligand (also referred to as a ‘complex-as-ligand’) is a
120 associated with a hexagon. This is, however, no different
metal complex that possesses peripheral donor atoms, allowing
from the scenario encountered in cyclohexane. If we view the
the complex to function as a ligand. Such complexes are partic-
metallohexagon in Scheme 21 as an analog of benzene (planar),
ularly useful as building blocks in larger arrays including metal–
then the metallohexagon depicted in Scheme 28 is an analog of
organic frameworks (MOFs).166 The synthesis and applications
cyclohexane (a chair conformation has been confirmed
of metalloligands comprise a mature field of coordination chem-
crystallographically).164 This and related observations132 under-
istry and the examples given in this section have been chosen to
line the fact that we are some way off fully understanding the
illustrate some of the basic principles behind their use.
principles of coordination polymer, network, and metallopoly-
One of the simplest ligands that may be incorporated into a
gon assemblies.
metalloligand is [CN]– because it is ambidentate, that is, it is
able to bind metal ions through either the C- or N-atom. Thus,
metal complexes of the type [M(CN)6]3– (M ¼ Fe, Cr) or
8.01.7 Taking Metallosquares into Three [M(CN)8]3– (M ¼ Mo, W) can be classed as metalloligands by
Dimensions through Ligand Design virtue of cyanido-bridge formation between metal centers.167
In metalloligands of the [M(CN)6]3– and [M(CN)8]3– families,
Scheme 20 illustrated that the combination of a {LPtII} ‘cor- all ligands within the inner coordination sphere of the metal-
ner’ with a ‘rigid-rod’ ligand results in the assembly of a molec- loligand are potential donors; the inclusion of domains that
ular square. Fujita has pioneered an extension of the concept to are incapable of binding a second metal ion (e.g., [W(bpy)
take the assemblies into three dimensions.165 The {(en)PdII} (CN)6]– as opposed to [W(CN)8]3–) lowers the dimensionality
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 17

OAc
OAc

O OAc
AcO
HN

O NH

8
O

FeCl2·4H2O
N N
N N +

N N

Predetermined metallohexacycle Unexpected metallopentacycle

OMe
FeCl2·4H2O
N N +
N N

N N

Predetermined metallohexacycle Unexpected metallopentacycle

Unexpected metalloheptacycle
Scheme 23 Designing building blocks for molecular hexagons: competition with unexpected products. Schematic representation: ligand, red;
metal node, blue.
18 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

OMe OMe
Stopper
unit

N N
Sonogashira
N N FeCl2·4H2O
coupling N N
Ru2+ Ru2+ [Fe6L6]24+
N N N N
N N

I I N N
N N

N N

Scheme 24 Designing building blocks for molecular hexagons with exocyclic metal-binding domains. Schematic representation: ligand, red; metal
node, blue.

of the final assembly.168 Platinum(II) complexes containing scaffold provides a strategy for development of MOFs having
{Pt2(m  S)2} cores, for example, L11, are among some of the achiral or chiral catalytically active centers immobilized on the
longest studied metalloligands,169 and cationic analogs, for MOF cavity walls.172,173 A variant on this chemistry is the forma-
example, L12, are also able to act as donors through the remain- tion of one- or two-dimensional coordination polymers which
ing free sulfur atom.170 use functionalized Schiff base complexes as metalloligand build-
ing blocks. The metalloligand L15 is a recent example; the periph-
+
S S eral oxamido and carboxylate groups bind first row d-block M2þ
(Ph3P)2Pt (Ph3P)2Pt R ions to give helical, one-dimensional chains and bind Cd2þ to
generate a two-dimensional coordination network.174 The incor-
(Ph3P)2Pt (Ph3P)2Pt poration of coordinatively unsaturated metal centers into the
S S pore walls of MOFs can also be achieved by using metallopor-
phyrins as the metalloligand building blocks and this approach
L11 [L12]+ has recently been reviewed.175

Another class of relatively simple metalloligands consists of

acyclic Schiff base complexes with appropriate donor groups.34
The metalloligand (i.e., the Schiff base complex) must be N N N N
designed so that its donor capabilities are spatially suited to Cu Cu
capturing a second metal ion. This is exemplified by comparing HO2C O O CO2H N O O N
the reactions of the ligands shown in Scheme 30 with Cu2þ or
Zn2þ. The cyclohexane-1,2-diyl backbone results in Cu2þ being L13 L14
in a square-planar environment and, as a consequence, the outer
OEt groups are preorganized to allow [CuL] to act as a metallo-
ligand with an O,O0 ,O00 ,O000 -donor set. By contrast, the sterically O O
hindered 1,10 -binaphthyl backbone forces the metal ion in [ML]
to be in a tetrahedral environment. As a result, the OEt groups are N N
directed well away from one another and the Schiff base complex Ni
- N N -
is no longer suited to facile formation of a dimetallic complex.171
O2C CO2
Other copper(II) Schiff base complexes developed for use as
metalloligands include L13 and L14; these exemplify a class of
metalloligand that acts as building blocks for MOFs with immo-
bilized copper(II) centers. Variation in metal ion and Schiff base L15
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 19

+ +
N N H2 MeCN NCMe
2+
N OTf
+ Pd + Pd
N N N OTf MeCN NCMe
H2

MeCN

H2N NH2 H2N NH2 H2N NH2

Pd Pd
Pd
N N N N N N

+N N+ +N N+ +N
N+
+N N+ +N
N+
+N
N+

N N N N N
N
Pd Pd
Pd
H2N NH2
N N N N

+N N+ +N N+
+N
+N N+ N+

N N N N
Pd Pd
H2N NH2 N N

+N
N+
+N
N+

N N
Pd
H2N NH2

Scheme 25 Formation of a dynamic library of interconnected molecular squares.

Methods for controlling the construction of MOFs include metal-binding capabilities of a smaller, organic counterpart.
the use of octahedral metal complexes functionalized with Two examples are given in Scheme 31. In the same way that
peripheral metal-binding domains. Metalloligands L16 and 4,40 -bipyridine functions as a rigid linker for the formation of
L17 are two representative examples.176,177 The choice of chiral coordination polymers (see Section 8.01.6), so too does [Ru
tris(chelate) complexes is particularly significant as it intro- (pytpy)2]2þ (pytpy ¼ bis{40 -(4-pyridyl)-2,20 :60 ,200 -terpyridine}),
duces chiral building blocks, either enantiopure or as a race- binding Agþ to give a one-dimensional chain in [{Ag(ONO2)
mate. The metalloligand L17 can be tuned by altering the (NCMe)(Ru(pytpy)2)}n]2nþ.181 Similarly, [Fe(pytpy)2]2þ binds
substitution pattern in the pyridine ring, by having one rather Cu2þ generating the coordination polymer [{Cu(OH2)
than two pendant pyridyl donors,178,179 or by altering the (O2NO)2(Fe(pytpy)2)}n]2nþ.182 Replacing the pendant pyridyl
central metal ion, for example, to Fe3þ.180 donors by pyrimidinyl domains produces a metalloligand
The concept of the ‘expanded ligand’ has been introduced4 suited to the construction of a two-dimensional array
to describe a metalloligand that topologically mimics the (Scheme 32); this is realized in the coordination network
20 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

HO2C
N

N O
N N N
O O
Co CO2H
Al
N N O O
N
N O

N
N
HO2C
L16 L17

[{[Ru(pyrtpy)2][CuCl2(OH2)][CuCl3]}n]nþ (pyrtpy ¼ 40 -(5- include {MNCO}n, {MNCN}n, and {MOCmO}n. The ring
pyrimidinyl)-2,20 :60 ,200 -terpyridine).183 More subtle changes sizes of metallacrowns range from 9 to 60 atoms designated
to the molecular architecture can be made by introducing 9-MC-3 to 60-MC-20; this nomenclature is analogous to that
spacers (e.g., hydrazone unit) between the {M(tpy)2}2þ unit of crown ethers, that is, 9-crown-3 to 60-crown-20. A wide
and the pendant metal-binding domains.184 variety of ligands is combined with metal ions from across
Examples of metalloligands that present pendant tpy or bpy the d-block to assemble metallacrowns,189 and Scheme 33
domains and are predicated upon linear gold(I) or square- summarizes the general prerequisites of the former, using b-
planar platinum(II) at their cores are L18–L20.185–187 The alanine hydroxamic acid as an example and the complexation
metalloligand L20 binds Fe2þ to give [n þ n] metallomacro- of its conjugate base with a metal ion, M2þ, to give an analog of
cycles in which n 2.187 12-crown-4.

N N
Au PPh2
N
(CH2)n
N Au PPh2
Au PPh2
N
N N N
Ph2P Au N

L18 L19 N

PR3
N N
Pt
N O PR3 O N

N N

L20

All of the examples so far in this section have involved 8.01.9 Ligand Design for Metal-Ion Extraction
metalloligands that possess peripheral metal-binding
[Link] Introduction
domains. Such complexes are used to expand assemblies. By
contrast, metallacrowns188–190 are analogs of crown ethers and An important trend in the industrial winning of metals is the
possess a binding domain for a metal ion, anion, or small development of environmentally benign and efficient tech-
molecule within the ligand cavity. The typical repeat unit of a nologies. Associated with this is the establishment of effi-
metallacrown is {MNO}n compared to the {CCO}n unit that is cient methodologies for the recycling of economically and
fundamental to a crown ether, but derivative metallacrowns strategically important metals. A key approach is hydromet-
are also known, for example, with general formulas which allurgy in which the traditional high-temperature processes
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 21

From the toolbox:

Self-assembly

Cu(OAc)2
MeO
N N N N
= Cu2+
N

phen tpy
Scheme 26 General principle of the assembly of interwoven metallocycles, exemplified by a triangular array, and an example of a ditopic ligand
designed to preferentially bind copper(II) in {Cu(phen)(tpy)} domains.

From the toolbox:

Self-assembly

[Cu(NCMe)4]+
N N N N
= Cu+

bpy bpy
Scheme 27 General principle of the assembly of a grid; each ligand has two metal-binding domains and in the example shown, these are equivalent
and bind copper(I) in a tetrahedral domain.

used in pyrometallurgy are replaced by aqueous and solvent- Established hydrometallurgical processes192 selectively target
extraction technologies. In this context, there has been sig- metal cations and transfer them from an aqueous to an
nificant effort expended on the design of ligands which will organic phase:
selectively and efficiently extract particular metals from pri-
nHLðorganic phaseÞ þ Mnþ ðaqÞP ½MLn ðorganic phaseÞ þ nHþ ðaqÞ
mary ores, spent ore, or waste191 and the development
of hydrometallurgical processes, for example, for copper The extraction of metal salts (instead of simply Mnþ) is
extraction, is now of major commercial significance.192 achieved by using zwitter-ionic ligands.193–196
22 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

Cl N
N N Cl
Zn Zn
N N
Cl Cl

N
N

ZnCl2 N N
Cl Zn Cl Cl Zn Cl
N N N
N N

N N

N Cl Cl
N
Zn Zn
N N
Cl Cl
N

Scheme 28 Serendipitous formation of a metallohexacycle with a ligand designed for coordination polymer assembly.

N
Pd
H2
N Pd
8 Pd2+ + 4 N N Pd Pd
N N Pd
H2
N N

Pd
Pd = {(en)Pd}2+
Scheme 29 Assembly of an octahedral Pd6L4 cage from {(en)PdII} units and 2,4,6-tris(4-pyridyl)-1,3,5-triazine.

In the following sections, we highlight selected, recent stabilizes the ligand pair is shown in red in Scheme 34. Intro-
(mainly post 2003)192 advances and research efforts in selective duction of substituents X which are hydrogen bond acceptors
recognition of metal ions, and in the design of ligands197–199 for (e.g., Cl and OMe) permits a second set of hydrogen-bonded
extraction and transport of metal ions. Computational interactions (shown in blue in Scheme 34) and their presence
approaches are becoming increasingly important in ligand design significantly enhances extraction of copper(II) ions.207
and prediction of stability constants for metal complexes.200–206 The compartmental macrocyclic ligand L21 is structurally
related to the receptor in Scheme 34 but binds two Cu2þ ions
(confirmed crystallographically). Ligand L21 has an extremely
[Link] Copper
high selectivity for Cu2þ with respect to Co2þ, Ni2þ, Zn2þ, Agþ,
Approximately 20–30% of the global copper production relies Cd2þ, and Pb2þ and extracting between aqueous and chloro-
on extraction processes involving salicyladoximine ligands. form phases;208 the use of ligands that can bind multiple Cu2þ
Hydrogen bonding plays a crucial role in preorganizing the ions increases the efficiency of extraction.209 Selective extrac-
ligands into pairs thereby generating a copper(II)-selective bind- tion and transport of Cu2þ are also observed with ligand HL22
ing site (Scheme 34). The primary hydrogen bonding that (Cu2 þ >> Zn2þ  Pb2þ  Ni2þ  Co2þ > Cd2þ > Mn2þ).210
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 23

N N
H
N
OH HO HO2C N
O
N N
HL22

HL21

N N N N N N
M2+ M M¢ n+ M
OH HO O O O O
M¢
O O O O O O

Binding pocket of the

metalloligand

N N M2+ N N
M
OH HO O O

O O O O

Four O donor atoms not

spatially suited to binding a
metal ion
Scheme 30 The spatial properties of an acyclic Schiff base ligand dictate whether the Schiff base metal complex can function as a metalloligand with
an O,O0 ,O00 ,O000 -donor set.

N 2+

N +
HO2C
CO2H
N HO2C CO2H N N
N N Cu
Ru HO2C N
CO2H N
N N N CO2H
N HO2C

Scheme 31 Examples of expanded ligands: the distance between the donor atoms is increased on going from the organic ligand to its metalloligand
counterpart, for example, from 7.1 to 18.3 Å on going from 4,40 -bpy to [Ru(pytpy)2]2þ.
24 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

N
N
M′ N N M2+ N N M′ Heterometallic one-dimensional chain
N
N

M′
M′ N
N N
N Heterometallic two-dimensional array
N M2+ N
N
N N
M′ N
M′

Scheme 32 Directed coordination patterns using metalloligands based on functionalized {M(tpy)2}2þ building blocks.

NH2 O
M
N NH2
N O M
OH O O O
−2H+ M2+
H2N HN H2N N O O
M O N
O H2N N
O M
O H2N

M N M
N
N O M O O O O
O M N
O N M
M O O O O O
N
N
M M N
12-crown-4
Scheme 33 Assembly of a metallacrown analog of 12-crown-4 through complex formation of the conjugate base of b-alanine hydroxamic acid with a
metal ion, M2þ.

 
X Mn þ ðaqÞ þ LHn ðRXÞn ðorgÞ LMðRXÞn ðorgÞ þ nHþ ðaqÞ
R 1 O H R 1 O H
N N O R Combinations of carboxylic or phosphinic acids and
Cu2+ Cu N3O2 -macrocyclic ligands have proved suited to efficient
2R OH R O N extraction of copper(II) ions.211
H O R1
X X
[Link] Gold, Palladium, and Platinum
Scheme 34 Hydrogen bonding is crucial to the success of
salicyladoximine ligands in selective extraction of copper(II) ions. See text. Understandably, much interest has centered upon the efficient
extraction of gold from primary ores and recycled materials. In
An alternative strategy to enhance metal-ion extraction general, metallic gold is oxidized to gold(I) and is coordinated
involves the use of combined organic acid/organic ligand by anions such as chloride or cyanide206 and the complexes are
assemblies, for example, proton transfer from acid to ligand then extracted using appropriate cations:
and inter-ion interactions (hydrogen bonds and electrostatic
interactions) that preorganize a supramolecular assembly: 2AuðsÞþ O2 þ 4½CN ðaqÞ þ 2H2 O

 ! 2 AuðCNÞ2 ðaqÞ þ H2 O2 ðaqÞ þ 2½OH
LðorgÞnRXH þ ðorgÞ LHn ðRXÞn ðorgÞ
However, the toxicity of cyanide is a major concern. Use of
where org is the organic phase. the thiocyanate ion in place of cyanide has been investi-
This assembly extracts metal ions through exchange of nHþ gated,212–216 and the application of pyrometallurgical, hydro-
for Mnþ, the position of the following equilibrium determining metallurgical, and bio-hydrometallurgical processes for the
the efficiency of extraction: extraction of gold from secondary sources has recently been
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 25

reviewed.217 There has also been some recent interest in the [Link] Cobalt, Nickel, and Zinc
design of ligands for gold. The selective extraction of palladium
Acid leaching of zinc, cobalt, and nickel is extensively used,
in the presence of gold and platinum, as well as of gold in the
and, for example, the greater thermodynamic stability of
presence of platinum, has been achieved using HL23, a ligand
[CoCl4]2– over [NiCl4]2– is a means of separating these two
previously widely used for extraction of first-row transition
metals.192 Selective extraction of [CoCl4]2– into phosphonium
metals. In the case of palladium, the intramolecularly
ionic liquids is an environmentally friendlier approach com-
hydrogen-bonded complex [Pd(L23)2] is implicated.218
pared to the separation of Co and Ni.222 Related to the outer-
sphere recognition of [PtCl6]2– described in Section [Link] is
that of [ZnCl4]2– and [CoCl4]2– using protonated amidopyr-
idine derivatives such as L26. The ligand [HL26]þ shows a high
N
OH selectivity for [MCl4]2– (M ¼ Zn, Co) over free chloride ion,
extracting the chloridometallate ions into organic phases
O OH through the formation of NH  Cl and CH  Cl
interactions.223 The protonated ligand H2L27 is preorganized
HL23 to capture both Zn2þ and [ZnCl4]2–. The Schiff base pocket
The increased applications of metal nanoparticles also lead which binds Zn2þ is decorated with pendant dihexylammo-
to potential problems of their removal from the environment nium domains, designed to bind [ZnCl4]2– through hydrogen
in the event of accidental discharge. Extraction of gold bond formation.224

N N
Zn
O O

+ +
O NH HN
Cl 2- Cl
N N Zn
H
Cl Cl
O N
H
L26
[ZnH2L27][ZnCl4]

nanoparticles from water into chloroform is assisted by 1- [Link] f-Block Metal Ions
dodecanethiol (i.e., a soft donor matching the soft gold) and
Similarities between the chemical properties of lanthanoid
the high recovery levels observed in both model and authentic
(Ln) and actinoid (An) metal ions result in significant
systems suggest that this approach has significant potential.219
challenges during the reprocessing of nuclear fuel waste. The
Recovery of platinum(IV) from acidic chloride streams used
ionic radii of all the Ln3þ ions are similar, and both Ln3þ and
in industry has been addressed using tripodal ligand receptors
An3þ are hard acids; ligands designed for their extraction
designed to target the [PtCl6]2– ion through hydrogen bond
involve hard donors (see Section [Link]). Progress in the
formation.220,221 Ligands also contain a bridgehead nitrogen
separation of f-block M3þ ions by solvent extraction was
atom that can be protonated so as to give a neutral
reviewed in 2010.225 After the separation of plutonium from
[HL]2[PtCl6] complex that is soluble in water-immiscible sol-
spent nuclear fuel using the PUREX (plutonium and uranium
vents. Ligands L24 and L25 are representative members of a
extraction) process, very small amounts of Am, Cm, and Np
family of 15 ligands designed for [PtCl6]2– recognition.
remain. Their separation from lanthanoid metal ions is real-
ized efficiently by using the phen derivative L28. This ligand
N N
O exhibits faster extraction kinetics than its bpy analog226
N O HN
O S because the rigid phen backbone preorganizes the ligand for
OMe
N O metal binding, in contrast to the need for the bpy ligand to
H undergo a trans-to-cis conformational change before coordi-
OMe
nation. The effects on extraction properties of decorating this
3 family of ligands with peripheral alkyl substituents have also
3
been detailed.227
L24 L25
26 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

an aqueous phase, catechol is used to extract the tris(chelate)

[Ge(O2C6H4)3]2– into an organic phase. Extraction efficiencies
of >90% are achieved and ligand recognition of Ge is selective
N N in the presence of As, Sb, Ni, V, Zn, and Mo.231,232 Given the
N N increased application of indium tin oxide (ITO) and the low
N N natural abundance of indium (ca. 240 ppb of the Earth’s crust),
N N recovery of indium from scrap electronic goods is topical.
Solvent extraction processes for indium are well developed
L28 for its separation from zinc ores in which it occurs; ligand L29
In contrast to the selective chelation of actinide(III) ions has a high selectivity for In in the presence of, for example,
described above, the TALSPEAK (trivalent actinide lanthanide Zn2þ, Fe2þ, Cd2þ, and Cu2þ after acid leaching. Acid (HCl or
separations by phosphorus-reagent extraction from aqueous H2SO4) leaching of ITO followed by extraction with L29 and/or
komplexes) process uses L29 to selectively target Ln3þ ions tributylphosphate is potentially a method of selectively recov-
and extract them into an organic phase while complexing ering Sn and In.233

OH
- HO O O OH
O O
+
P N
O O N N
OH HO OH

L29 O O
L30

An3þ ions with L30 in the aqueous phase. This procedure has 8.01.10 Conclusion
been adapted to use ionic liquids in place of conventional
organic media, with high extraction efficiencies and metal- This brief overview serves to emphasize that the design of
ion selectivities being observed.228 ligands for the specific binding of specific single or multiple
The tripodal ligand L31 is highly selective toward 147Pm3þ metal centers has reached a high degree of sophistication and
in the presence of other Ln3þ ions; the metal ions are intro- mastery and is an active area that is constantly facing and
duced as picrate salts in aqueous solution and extracted by L31 addressing new challenges. The practitioners of this new art
into an organic phase. The ligand is designed to accept the of ligand design are masters not only of both organic and
metal ion into a bowl-like receptor, and crystallographic stud- inorganic synthetic methods but also increasingly of the aes-
ies of representative complexes confirm that L31 binds Ln3þ in thetics of molecular beauty. For related chapters in this Com-
a heptadentate mode; for Ln ¼ La, two picrate ions are also prehensive, we refer to Chapters 5.04 and 8.02.
coordinated, while only one is present in the inner coordina-
tion sphere for Ln ¼ Gd or Er.229 Compound L32 is representa-
tive of a family of tripodal ligands in which three
References
carbamoylmethylphosphane oxide arms are preorganized for 1. Seidel, S.; Seppelt, K. Science 2000, 290, 117–118.
metal binding, specifically An4þ ions; the properties of the 2. Kubas, G. J. Metal Dihydrogen and s-Bond Complexes. Kluwer Academic/
ligands (e.g., solubility) are tuned by altering substituents R1 Plenum: New York, 2001.
3. Constable, E. C. Pure Appl. Chem. 1996, 68, 253–260.
and R2 and by changing the lengths of the three arms. High
4. Constable, E. C. Coord. Chem. Rev. 2008, 252, 842–855.
selectivity toward Pu4þ is achieved, with concomitant low 5. Pearson, R. G. Chemical Hardness. Wiley-VCH: Weinheim, 1997.
affinity for M3þ ions.230 6. Martell, A. E.; Hancock, R. D.; Motekaitis, R. J. Coord. Chem. Rev. 1994, 133,
39–65.
7. Gerloch, M.; Constable, E. C. Transition Metal Chemistry. VCH: Weinheim, 1994.
H +
N 8. Martell, A. E.; Smith, R. M. Critical Stability Constants; Plenum Press: New York,
O P 1975; Vol. 1.
HC R1 O O-
9. Blackman, A. G. Compt. Rend. Chim. 2005, 8, 107–119.
N N
O 10. Constable, E. C. Prog. Inorg. Chem. 1994, 42, 67–138.
11. Martell, A. E.; Hancock, R. D. Metal Complexes in Aqueous Solutions. Plenum
O 3
R2 3 Press: New York, 1996.
31 32 12. Constable, E. C. Coordination Compounds of Macrocyclic Compounds. Oxford
L L
University Press: Oxford, 1999.
13. Alexeeva, Y. E.; Kharisov, B. I.; Hernández Garcı́a, T. C.; Garnovskii, A. D. Coord.
Chem. Rev. 2010, 254, 794–831.
14. Constable, E. C.; Harverson, P.; Housecroft, C. E.; Nordlander, E.; Olsson, J.
[Link] p-Block Metal Ions Polyhedron 2006, 25, 437–458.
15. Constable, E. C.; Figgemeier, E.; Housecroft, C. E.; Olsson, J.; Zimmermann, Y. C.
Hydrometallurgical processes for the recovery of p-block metal
J. Chem. Soc. Dalton Trans. 2004, 13, 1918–1927.
ions are illustrated with the extraction of Ge(IV) from fly ash 16. Suzuki, A. In Metal-Catalyzed Cross-Coupling Reactions; Diederich, F.,
produced industrially in coal gasification. After leaching into Stang, P. J., Eds.; Wiley-VCH: New York, 1998; pp 49–97.
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 27

17. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457–2483. 61. Amabilino, D. B.; Sauvage, J.-P. Templated Synthesis of Knots and Ravels.
18. Suzuki, A. J. Organometallic Chem. 1999, 576, 147–168. In Steed, J. W., Gale, P. A., Eds.; Supramolecular Chemistry: From Molecules to
19. Gütz, C.; Lützen, A. Synthesis 2010, 85–90. Nanomaterials; Wiley: Weinheim, 2012; Vol. 5, pp 2245–2262.
20. Farina, V.; Krishnamurthy, V.; Scott, W. J. Org. React. 1998, 50, 1–652. 62. Yuan, Z.-L.; Zhang, Q.-L.; Liang, X.; Zhu, B.-X.; Lindoy, L. F.; Wei, G. Polyhedron
21. Mitchell, T. N. In Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., 2008, 27, 344–348.
Stang, P. J., Eds.; Wiley-VCH: New York, 1998; pp 167–202. 63. Curtis, N. F. In McCleverty, J. A., Meyer, T. J., Eds.; Comprehensive Coordination
22. Farina, V.; Krishnamurthy, V.; Scott, W. J. The Stille Reaction. John Wiley & Sons: Chemistry II; Elsevier: Oxford, 2003; Vol. 1, pp 447–474.
New York, 1998. 64. Smith, K. M. In McCleverty, J. A., Meyer, T. J., Eds.; Comprehensive Coordination
23. Heller, M.; Schubert, U. S. J. Org. Chem. 2002, 67, 8269–8272. Chemistry II; Elsevier: Oxford, 2003; Vol. 1, pp 493–506.
24. Sonogashira, K. J. Organomet. Chem. 2002, 653, 46–49. 65. Junk, P. C. New J. Chem. 2008, 32, 762–773.
25. Hwang, S.-H.; Moorefield, C. N.; Fronczek, F. R.; Lukoyanova, O.; Echegoyen, L.; 66. Levason, W.; Reid, G. In McCleverty, J. A., Meyer, T. J., Eds.; Comprehensive
Newkome, G. R. Chem. Commun. 2005, 713–715. Coordination Chemistry II; Elsevier: Oxford, 2003; Vol. 1, pp 475–484.
26. Kolb, H. C.; Sharpless, K. B. Drug Discov. Today 2003, 8, 1128. 67. Swor, C. D.; Tyler, D. R. Coord. Chem. Rev. 2011, 255, 2860–2881.
27. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem. Int. Ed. 2001, 40, 68. Pascariu, A.; Iliescu, S.; Popa, A.; Ilia, G. J. Organomet. Chem. 2009, 694,
2004–2021. 3982–4000.
28. Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew. Chem. Int. 69. Grant, G. J. Struct. Bond. 2006, 120, 107–141.
Ed. 2002, 41, 2596–2599. 70. Levason, W.; Reid, G. In McCleverty, J. A., Meyer, T. J., Eds.; Comprehensive
29. Stengel, I.; Mishra, A.; Pootrakulchote, N.; Moon, S.-J.; Zakeeruddin, S. M.; Coordination Chemistry II; Elsevier: Oxford, 2003; Vol. 1, pp 399–410.
Grätzel, M.; Bäuerle, P. J. Mater. Chem. 2011, 21, 3726–3734. 71. Levason, W.; Reid, G. In Steed, J. W., Gale, P. A., Eds.; Supramolecular
30. Constable, E. C.; Housecroft, C. E.; Price, J. R.; Schweighauser, L.; Zampese, J. A. Chemistry: From Molecules to Nanomaterials; Wiley: Weinheim, 2012; Vol. 3,
Inorg. Chem. Commun. 2010, 13, 495–497. pp 785–810.
31. Constable, E. C.; Housecroft, C. E.; Neuburger, M.; Rösel, P. Chem. Commun. 72. Levason, W.; Reid, G.; Zhang, W. Dalton Trans. 2011, 40, 8491–8506.
2010, 46, 1628–1630. 73. Panda, A. Coord. Chem. Rev. 2009, 253, 1056–1098.
32. Stengel, I.; Strassert, C. A.; Plummer, E. A.; Chien, C. H.; De Cola, L.; Bäuerle, P. 74. Fabbrizzi, L.; Licchelli, M.; Mosca, L.; Poggi, A. Coord. Chem. Rev. 2010, 254,
Eur. J. Inorg. Chem. 2012, 1795–1809. 1628–1636.
33. Schiff, H. Ann. Chem. 1864, (supplement 3), 343. 75. Thompson, M. C.; Busch, D. H. J. Am. Chem. Soc. 1964, 86, 3651–3656.
34. Sreenivasulu, B. In Supramolecular Chemistry: From Molecules to Nanomaterials; 76. Barefield, E. K. Inorg. Chem. 1972, 11, 2273–2274.
Steed, J. W., Gale, P. A., Eds.; Wiley: Weinheim, 2012; Vol. 3, pp 827–862. 77. Hernández-Molina, R.; Mederos, A. In McCleverty, J. A., Meyer, T. J., Eds.;
35. Costisor, O.; Saity, L.; Linert, W. Revs. Inorg. Chem. 2005, 25, 285–347. Comprehensive Coordination Chemistry II; Elsevier: Oxford, 2003; Vol. 1,
36. Whiteoak, C. J.; Salassa, G.; Kleij, A. W. Chem. Soc. Rev. 2012, 41, 622–631. pp 411–446.
37. Castilla, A. M.; Curreli, S.; Escudero-Adán, E. C.; Belmonte, M. M.; Benet- 78. Vigato, P. A.; Tamburini, S.; Bertolo, L. Coord. Chem. Rev. 2007, 251,
Buchholz, J.; Kleij, A. W. Org. Lett. 2009, 11, 5218–5221. 1311–1492.
38. Constable, E. C.; Zhang, G.; Housecroft, C. E.; Neuburger, M.; Zampese, J. A. Eur. 79. Vigato, P. A.; Peruzzo, V.; Tamburini, S. Coord. Chem. Rev. 2012, 256,
J. Inorg. Chem. 2010, 2000–2011. 953–1114.
39. Che, C.-M.; Huang, J.-S. Coord. Chem. Rev. 2003, 242, 97–113. 80. Brooker, S. Coord. Chem. Rev. 2001, 222, 33–56.
40. Caputo, C. A.; Jones, N. D. Dalton Trans. 2007, 4627–4640. 81. Vigato, P. A.; Tamburini, S. Coord. Chem. Rev. 2004, 248, 1717–2128.
41. Chatterjee, D. Coord. Chem. Rev. 2008, 252, 176–198. 82. Radecka-Paryzek, W.; Patroniak, V.; Lisowski, J. Coord. Chem. Rev. 2005, 249,
42. Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 2156–2175.
2247–2250. 83. Castellato, U.; Tamburini, S.; Tomasin, P.; Vigato, P. A. Inorg. Chim. Acta 2004,
43. Weck, M.; Mohr, B.; Sauvage, J. P.; Grubbs, R. H. J. Org. Chem. 1999, 64, 357, 4191–4207.
5463–5471. 84. Suzuki, M.; Furutachi, H.; Okawa, H. Coord. Chem. Rev. 2000, 200–202,
44. Mohr, B.; Weck, M.; Sauvage, J. P.; Grubbs, R. H. Angew. Chem. Int. Ed. 1997, 105–129.
36, 1308–1310. 85. Caneschi, A.; Sorace, L.; Castellato, U.; Tomasin, P.; Vigato, P. A. Eur. J. Inorg.
45. Dietrich-Buchecker, C.; Rapenne, G.; Sauvage, J. P. Chem. Commun. 1997, Chem. 2004, 3887–3900.
2053–2054. 86. Tamburini, S.; Peruzzo, V.; Benetollo, F.; Vigato, P. A. Eur. J. Inorg. Chem. 2010,
46. Dietrich-Buchecker, C.; Rapenne, G.; Sauvage, J. P. Coord. Chem. Rev. 1999, 1853–1863.
185–186, 167–176. 87. Feltham, H. L. C.; Brooker, S. Coord. Chem. Rev. 2009, 253, 1458–1475.
47. Leigh, D. A.; Lusby, P. J.; McBurney, R. T.; Morelli, A.; Slawin, A. M. Z.; 88. Akine, S.; Taniguchi, T.; Nabeshima, T. Tetrahedron Lett. 2001, 42, 8861–8864.
Thomson, A. R.; Walker, D. B. J. Am. Chem. Soc. 2009, 131, 3762–3771. 89. Akine, S.; Sunaga, S.; Taniguchi, T.; Miyazaki, H.; Nabeshima, T. Inorg. Chem.
48. Song, K. H.; Kang, S. O.; Ko, J. Chem. Eur. J. 2007, 13, 5129–5134. 2007, 46, 2959–2961.
49. Kawano, T.; Nakanishi, M.; Kato, T.; Ueda, I. Chem. Lett. 2005, 34, 350–351. 90. Meyer, C. D.; Joiner, C. S.; Stoddart, J. F. Chem. Soc. Rev. 2007, 36,
50. Chuchuryukin, A. V.; Chase, P. A.; Dijkstra, H. P.; Suijkerbuijk, B. M. J. M.; 1705–1723.
Mills, A. M.; Spek, A. L.; van Klink, G. P. M.; van Koten, G. Adv. Synth. Catal. 91. Jiang, J.-C.; Chu, Z.-L.; Huang, W.; Wang, G.; You, X.-Z. Inorg. Chem. 2010, 49,
2005, 347, 447–462. 5897–5911.
51. Wang, P.; Moorefield, C. N.; Newkome, G. R. Angew. Chem. Int. Ed. 2005, 44, 92. Edwards, P. G.; Hahn, F. E. Dalton Trans. 2011, 40, 10278–10288.
1679–1683. 93. Hahn, F. E.; Langenhahn, V.; Lügger, T.; Pape, T.; Le Van, D. Angew. Chem. Int.
52. Laemmel, A.-C.; Collin, J.-P.; Sauvage, J.-P.; Accorsi, G.; Armaroli, N. Eur. J. Ed. 2005, 44, 3759–3763.
Inorg. Chem. 2003, 467–474. 94. Li, C.-K.; Lu, X.-X.; Wong, K. M.-C.; Chan, C.-L.; Zhu, N.; Yam, V. W.-W. Inorg.
53. Sauvage, J. P.; Ward, M. Inorg. Chem. 1991, 30, 3869–3874. Chem. 2004, 43, 7421–7430.
54. Mobian, P.; Kern, J. M.; Sauvage, J. P. Angew. Chem. Int. Ed. 2004, 43, 95. Wong, K. M.-C.; Yam, V. W.-W. Coord. Chem. Rev. 2007, 251,
2392–2395. 2477–2488.
55. Chambron, J. C.; Collin, J.-P.; Heitz, V.; Jouvenot, D.; Kern, J. M.; Mobian, P.; 96. Timmons, J. C.; Hubin, T. J. Coord. Chem. Rev. 2010, 254, 1661–1685.
Pomeranc, D.; Sauvage, J.-P. Eur. J. Org. Chem. 2004, 1627–1638. 97. Stang, P. J.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502–518.
56. de Sousa Healy, M.; Rest, A. J. Adv. Inorg. Chem. Radiochem. 1978, 21, 1–40. 98. Leininger, S.; Olenyuk, B.; Stang, P. J. Chem. Rev. 2000, 100, 853–908.
57. Costisor, O.; Linert, W. Metal Mediated Template Synthesis of Ligands. World 99. Seidel, S. R.; Stang, P. J. Acc. Chem. Res. 2002, 35, 972–983.
Scientific Pub Co. Inc.: Singapore, 2004. 100. Northrop, B. H.; Yang, H.-B.; Stang, P. J. Chem. Commun. 2008,
58. Constable, E. C. Coordination Chemistry of Macrocyclic Ligands. Oxford 5896–5908.
University Press: Oxford, 1999. 101. Yoshizawa, M.; Klosterman, J. K.; Fujita, M. Angew. Chem. Int. Ed. 2009, 48,
59. Amabilino, D. B. Template Strategies in Self-Assembly. In Steed, J. W., 3418–3438.
Gale, P. A., Eds.; Supramolecular Chemistry: From Molecules to Nanomaterials; 102. Constable, E. C.; Cargill Thompson, A. M. W. J. Chem. Soc. Dalton Trans. 1992,
Wiley: Weinheim, 2012; Vol. 5, pp 1967–1992. 3467–3475.
60. Gerbeleu, N. V.; Arion, V. B.; Burgess, J. Template Synthesis of Macrocyclic 103. Liu, C.-M.; Zhang, D.-Q.; Zhu, D.-B. Cryst. Growth Des. 2006, 6, 524–529.
Compounds. Wiley: Weinheim, 1994. 104. Adarsh, N. N.; Dastidar, P. Chem. Soc. Rev. 2012, 41, 3039–3060.
28 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies

105. Wang, X.-S.; Tang, Y.-Z.; Huang, X.-F.; Qu, Z.-R.; Che, C.-M.; Chan, P. W. H.; 148. Chan, Y.-T.; Li, X.; Soler, M.; Wang, J.-L.; Wesdemiotis, C.; Newkome, G. R.
Xiong, R.-G. Inorg. Chem. 2005, 44, 5278–5285. J. Am. Chem. Soc. 2009, 131, 16395–16397.
106. Kelch, S.; Rehahn, M. Chem. Commun. 1999, 1123–1124. 149. Hwang, S.-H.; Wang, P.; Moorefield, C. N.; Jung, J.-C.; Kim, J.-Y.; Lee, S.-W.;
107. Kelch, S.; Rehahn, M. Macromolecules 1999, 32, 5818–5828. Newkome, G. R. Macromol. Rapid Comm. 2006, 27, 1809–1813.
108. Chiper, M.; Hoogenboom, R.; Schubert, U. Macromol. Rapid Commun. 2009, 150. Chan, Y.-T.; Moorefield, C. N.; Soler, M.; Newkome, G. R. Chem. Eur. J. 2010,
30, 565–578. 16, 1768–1771.
109. Constable, E. C.; Harris, K.; Housecroft, C. E.; Nauburger, M. Dalton Trans. 2011, 151. Chan, Y.-T.; Li, X.; Moorefield, C. N.; Wesdemiotis, C.; Newkome, G. R. Chem.
40, 1524–1534. Eur. J. 2011, 17, 7750–7754.
110. Friese, V. A.; Kurth, D. G. Coord. Chem. Rev. 2008, 252, 199–211. 152. Eryazici, I.; Newkome, G. R. New J. Chem. 2009, 33, 345–357.
111. Kurth, D. G.; Higuchi, M. Soft Matter 2006, 2, 915–927. 153. Li, S.; Moorefield, C. N.; Shreiner, C. D.; Wang, P.; Sarkar, R.; Newkome, G. R.
112. Friese, V. A.; Kurth, D. G. Curr. Opinion Colloid Interface Sci. 2009, 14, 81–93. New J. Chem. 2011, 35, 2130–2135.
113. Yu, S.-C.; Kwok, C.-C.; Chan, W.-K.; Che, C.-M. Adv. Mater. 2003, 15, 154. Constable, E. C.; Housecroft, C. E.; Neuburger, M.; Rösel, P. J.; Schaffner, S.;
1643–1647. Zampese, J. A. Chem. Eur. J. 2009, 15, 11746–11757.
114. Han, F. S.; Higuchi, M.; Kurth, D. G. Adv. Mater. 2007, 19, 3928–3931. 155. Li, S.; Moorefield, C. N.; Wang, P.; Schriner, C. D.; Newkome, G. R. Eur. J. Org.
115. Siebert, R.; Winter, A.; Schmitt, M.; Popp, J.; Schubert, U. S.; Dietzek, B. Chem. 2008, 3328–3334.
Macromol. Rapid Commun. 2012, 33, 481–497. 156. Blanco, V.; Garcı́a, M. D.; Platas-Iglesias, C.; Peinador, C.; Quintela, J. M. Chem.
116. Han, F. S.; Higuchi, M.; Akasaka, Y.; Otsuka, Y.; Kurth, D. G. Thin Solid Films Commun. 2010, 46, 6672–6674.
2008, 516, 2469–2473. 157. Swiegers, G. F.; Malefeste, T. J. Chem. Rev. 2000, 100, 3483–3537.
117. Han, F. S.; Higuchi, M.; Kurth, D. G. J. Am. Chem. Soc. 2008, 130, 2073–2081. 158. Coronado, E.; Galan-Mascaros, J. R.; Gaviña, P.; Martı́-Gastaldo, C.;
118. Schwarz, G.; Bodenthin, Y.; Tomkowicz, Z.; Haase, W.; Geue, T.; Kohlbrecher, J.; Romero, F. M.; Tatay, S. Inorg. Chem. 2008, 47, 5197–5203.
Pietsch, U.; Kurth, D. G. J. Am. Chem. Soc. 2011, 133, 547–558. 159. Glasson, C. R. K.; Lindoy, L. F.; Meehan, G. V. Coord. Chem. Rev. 2008,
119. Winter, A.; Hoeppener, S.; Newkome, G. R.; Schubert, U. S. Adv. Mater. 2011, 23, 252, 940–963.
3484–3498. 160. Stefankiewicz, A. R.; Rogez, G.; Harrowfield, J.; Drillon, M.; Lehn, J.-M. Dalton
120. Winter, A.; Hager, M. D.; Newkome, G. R.; Schubert, U. S. Adv. Mater. 2011, Trans. 2009, 5787–5802.
23, 5728–5748. 161. Patroniak, V.; Stefankiewicz, A. R.; Lehn, J.-M.; Kubicki, M. Eur. J. Inorg. Chem.
121. Wild, A.; Winter, A.; Schlütter, F.; Schubert, U. S. Chem. Soc. Rev. 2011, 40, 2005, 4168–4173.
1459–1511. 162. Ruben, M.; Rojo, J.; Romero-Salguero, F. J.; Uppadine, L. H.; Lehn, J.-M. Angew.
122. Beck, J. B.; Rowan, S. J. J. Am. Chem. Soc. 2003, 125, 13922–13923. Chem. Int. Ed. 2004, 43, 3644–3662.
123. Weng, W.; Beck, J. B.; Jamieson, A. M.; Rowan, S. J. J. Am. Chem. Soc. 2006, 163. Baxter, P. N. W.; Lehn, J.-M.; Kneisel, B. O.; Fenske, D. Chem. Commun. 1997,
128, 11663–11672. 2231–2232.
124. Weng, W.; Li, Z.; Jamieson, A. M.; Rowan, S. J. Soft Matter 2009, 5, 164. Constable, E. C.; Zhang, G.; Housecroft, C. E.; Zampese, J. A. CrystEngComm
4647–4657. 2011, 13, 6864–6870.
125. Burnworth, M.; Rowan, S. J.; Weder, C. Macromolecules 2011, 45, 126–132. 165. Fujita, M.; Tominaga, M.; Hori, A.; Therrien, B. Acc. Chem. Res. 2005, 38,
126. Whittell, G. R.; Hager, M. D.; Schubert, U. S.; Manners, I. Nature Mater. 2011, 10, 371–380.
176–188. 166. Garibay, S. J.; Stork, J. R.; Cohen, S. M. Prog. Inorg. Chem. 2009, 56,
127. Barquı́n, M.; Cancela, J.; González Garmendia, M. J.; Quintanilla, J.; Amador, U. 335–378.
Polyhedron 1998, 17, 2373–2378. 167. Shatruk, M.; Avendano, C.; Dunbar, K. R. Prog. Inorg. Chem. 2009, 56,
128. Cave, G. W. V.; Raston, C. L. J. Supramol. Chem. 2002, 2, 317–319. 155–334.
129. Hou, L.; Li, D. Inorg. Chem. Comm. 2005, 8, 190–193. 168. Alexandru, M.-G.; Visinescu, D.; Madalan, A. M.; Lloret, F.; Julve, M.; Andruh, M.
130. Li, X.-Z.; Li, M.; Li, Z.; Hou, J.-Z.; Huang, X.-C.; Li, D. Angew. Chem. Int. Ed. Inorg. Chem. 2012, 51, 4906–4908.
2008, 47, 6371–6374. 169. Gonzáles-Duarte, P.; Lledós, A.; Mas-Ballesté, R. Eur. J. Inorg. Chem. 2004,
131. Constable, E. C.; Zhang, G.; Housecroft, C. E.; Neuburger, M.; Zampese, J. A. 3585–3599.
CrystEngComm. 2010, 12, 2146–2152. 170. Henderson, W.; Nicholson, B. K.; Devoy, S. M.; Hor, T. S. A. Inorg. Chim. Acta
132. Heine, J.; Schmedt auf der Günne, J.; Dehnen, S. J. Am. Chem. Soc. 2011, 133, 2008, 361, 1908–1914.
10018–10021. 171. Constable, E. C.; Zhang, G.; Housecroft, C. E.; Neuburger, M.; Zampese, J. A.
133. Constable, E. C.; Zhang, G.; Coronado, E.; Housecroft, C. E.; Neuburger, M. Inorg. Chim. Acta 2010, 363, 4207–4213.
CrystEngComm. 2010, 12, 2139–2145. 172. Das, M. C.; Xiang, S.; Zhang, Z.; Chen, B. Angew. Chem. Int. Ed. 2011, 50,
134. Constable, E. C.; Housecroft, C. E.; Neuburger, M.; Vujovic, S.; Zampese, J. A.; 10510–10520.
Zhang, G. CrystEngComm. 2012, 14, 3554–3563. 173. Thanasekaran, P.; Luo, T.-T.; Wu, J.-Y.; Lu, K.-L. Dalton Trans. 2012, 41,
135. Batten, S. R.; Neville, S. M.; Turner, D. R. Coordination Polymers: Design 5437–5453.
Analysis and Application. RSC Publishing: Cambridge, 2008. 174. Li, X.-Z.; Hao, P.-P.; Wang, D.; Zhang, W.-Q.; Zhu, L.-N. CrystEngComm 2012,
136. Han, L.; Hong, M. Inorg. Chem. Comm. 2005, 8, 406–419. 14, 366–369.
137. Imaz, I.; Maspoch, D. In Steed, J. W., Gale, P. A., Eds.; Supramolecular Chemistry: 175. Burnett, B. J.; Barron, P. M.; Choe, W. CrystEngComm 2012, 14, 3839–3846.
From Molecules to Nanomaterials; Wiley: Weinheim, 2012; Vol. 5, 176. Garibay, S. J.; Stork, J. R.; Wang, Z.; Cohen, S. M.; Telfer, S. G. Chem. Commun.
pp 2045–2069. 2007, 4881–4883.
138. Han, L.; Hong, M. Inorg. Chem. Commun. 2005, 8, 406–419. 177. Burrows, A. D.; Frost, C. G.; Mahon, M. F.; Raithby, P. R.; Renouf, C. L.;
139. Swiegers, G. F.; Malefetse, T. J. Chem. Eur. J. 2001, 7, 3636–3643. Richardson, C.; Stevenson, A. J. Chem. Commun. 2010, 46, 5067–5069.
140. Swiegers, G. F.; Malefetse, T. J. Coord. Chem. Rev. 2002, 225, 91–121. 178. Burrows, A. D.; Mahon, M. F.; Renouf, C. L.; Richardson, C.; Warren, A. J.;
141. Northrop, B. H.; Zheng, Y.-R.; Chi, K.-W.; Stang, P. J. Acc. Chem. Res. 2009, Warren, J. E. Dalton Trans. 2012, 41, 4153–4163.
42, 1554–1563. 179. Wu, H.-B.; Wang, Q.-M. Angew. Chem. Int. Ed. 2009, 48, 7343–7345.
142. Stang, P. J.; Cao, D. H.; Saito, S.; Arif, A. M. J. Am. Chem. Soc. 1995, 117, 180. Carlucci, L.; Ciani, G.; Proserpio, D. M.; Visconti, M. CrystEngComm 2011,
6273. 13, 5891–5902.
143. Liu, X.; Stern, C. L.; Mirkin, C. A. Organometallics 2002, 21, 1017–1019. 181. Beves, J.; Constable, E. C.; Housecroft, C. E.; Kepert, C.; Price, D. J.
144. Chakrabarty, R.; Mukherjee, P. S.; Stang, P. J. Chem. Rev. 2011, 111, CrystEngComm 2007, 9, 456–459.
6810–6918. 182. Beves, J.; Constable, E. C.; Housecroft, C. E.; Neuburger, M.; Schaffner, S.
145. Newkome, G. R.; Cho, T. J.; Moorefield, C. N.; Cush, R.; Russo, P. S.; CrystEngComm 2008, 10, 344–348.
Godı́nez, L. A.; Saunders, M. J.; Mohapatra, P. Chem. Eur. J. 2002, 8, 183. Beves, J.; Constable, E. C.; Decurtins, S.; Dunphy, E. L.; Housecroft, C. E.;
2946–2954. Keene, T. D.; Neuburger, M.; Schaffner, S. CrystEngComm 2008, 10,
146. Soler, M.; Moorefield, C. N.; Newkome, G. R. Adv. Heterocyclic Chem. 2010, 986–990.
101, 1–74. 184. Beves, J. E.; Constable, E. C.; Housecroft, C. E.; Kepert, C. J.; Neuburger, M.;
147. Newkome, G. R.; Wang, P.; Moorefield, C. N.; Cho, T. J.; Mohapatra, P. P.; Li, S.; Price, D. J.; Schaffner, S.; Zampese, J. A. Dalton Trans. 2008, 6742–6751.
Hwang, S.-H.; Lukoyanova, O.; Echegoyen, L.; Palagallo, J. A.; Iancu, V.; 185. Vicente, J.; Gil-Rubio, J.; Barquero, N.; Jones, P. G.; Bautista, D. Organometallics
Hla, S. W. Science 2006, 312, 1782–1785. 2008, 27, 646–659.
 Ligand and Metalloligand Design for Macrocycles, Multimetallic Arrays, Coordination Polymers, and Assemblies 29

186. Constable, E. C.; Housecroft, C. E.; Kocik, M. K.; Zampese, J. A. Polyhedron 210. Tasaki, T.; Oshima, T.; Baba, Y. Talanta 2007, 73, 387–393.
2011, 30, 2704–2710. 211. Byriel, K. A.; Gasperov, V.; Gloe, K.; Kennrd, C. H. L.; Leong, A. J.; Lindoy, L. F.;
187. Beves, J. E.; Constable, E. C.; Housecroft, C. E.; Neuburger, M.; Schaffner, S.; Mahinay, M. S.; Pham, H. T.; Tasker, P. A.; Thorp, D.; Turner, P. Dalton Trans.
Shardlow, E. J. Dalton Trans. 2007, 1593–1602. 2003, 3034–3040.
188. Pecoraro, V. L.; Stemmler, A. J.; Gibney, B. R.; Bodwin, J. J.; Wang, H.; 212. Li, J.; Safarzadeh, M. S.; Moats, M. S.; Miller, J. D.; LeVier, K. M.; Dietrich, M.;
Kampf, J. W.; Barwinski, A. Prog. Inorg. Chem. 1997, 45, 83–177. Wan, R. W. Hydrometallurgy 2012, 113–114, 1.
189. Mezei, G.; Zaleski, C. M.; Pecoraro, V. L. Chem. Rev. 2007, 107, 4933–5003. 213. Li, J.; Safarzadeh, M. S.; Moats, M. S.; Miller, J. D.; LeVier, K. M.; Dietrich, M.;
190. Tegoni, M.; Remelli, M. Coord. Chem. Rev. 2012, 256, 289–315. Wan, R. W. Hydrometallurgy 2012, 113–114, 10.
191. Habashi, F. J. Min. Metall. Sect. B 2009, 45, 1–13. 214. Li, J.; Safarzadeh, M. S.; Moats, M. S.; Miller, J. D.; LeVier, K. M.; Dietrich, M.;
192. Tasker, P. A.; Plieger, P. G.; West, L. C. In McCleverty, J. A., Meyer, T. J., Eds.; Wan, R. W. Hydrometallurgy 2012, 113–114, 19.
Comprehensive Coordination Chemistry II; Elsevier: Oxford, 2003; Vol. 9, 215. Li, J.; Safarzadeh, M. S.; Moats, M. S.; Miller, J. D.; LeVier, K. M.; Dietrich, M.;
pp 759–808. Wan, R. W. Hydrometallurgy 2012, 113–114, 25.
193. Tasker, P. A.; Tong, C. C.; Westra, A. N. Coord. Chem. Rev. 2007, 251, 1868. 216. Li, J.; Safarzadeh, M. S.; Moats, M. S.; Miller, J. D.; LeVier, K. M.; Dietrich, M.;
194. Coxall, R. A.; Lindoy, L. F.; Miller, H. A.; Parkin, A.; Parsons, S.; Tasker, P. A.; Wan, R. W. Hydrometallurgy 2012, 113–114, 31.
White, D. J. Dalton Trans. 2003, 55–64. 217. Syed, S. Hydrometallurgy 2012, 115–116, 30–51.
195. Forgan, R. J.; Davidson, J. E.; Fabbiani, F. P. A.; Galbraith, S. G.; 218. Shen, Y. F.; Xue, W. Y. Sep. Purif. Technol. 2007, 56, 278–283.
Henderson, D. K.; Moggach, S. A.; Parsons, S.; Tasker, P. A.; White, F. J. Dalton 219. Li, L.; Leopold, K. Anal. Chem. 2012, 84,
Trans. 2010, 39, 1763–1770. 4340–4349.
196. Forgan, R. J.; Davidson, J. E.; Galbraith, S. G.; Henderson, D. K.; Parsons, S.; 220. Warr, R. J.; Westra, A. N.; Bell, K. J.; Chartes, J.; Ellis, R.; Tong, C.;
Tasker, P. A.; White, F. J. Chem. Commun. 2008, 4049–4051. Simmance, T. G.; Gadzhieva, A.; Blake, A. J.; Tasker, P. A.; Schröder, M. Chem.
197. Galbraith, S. G.; Tasker, P. A. Supramol. Chem. 2005, 17, 191–207. Eur. J. 2009, 15, 4836–4850.
198. Tasker, P. A.; Gasperov, V. In Macrocyclic Chemistry; Gloe, K., Ed.; Springer: 221. Bell, K. J.; Westra, A. N.; Warr, R. J.; Chartes, J.; Ellis, R.; Tong, C.; Blake, A. J.;
Dordrecht, 2005; pp 365–382. Tasker, P. A.; Schröder, M. Angew. Chem. Int. Ed. 2008, 47, 1745–1748.
199. Kaye, P. T. S. Afr. J. Sci. 2011, 107, 23–30. 222. Wellens, S.; Thijs, B.; Binnemans, K. Green Chem. 2012, 14, 1657–1665.
200. Varnek, A.; Fourches, D.; Kireeva, N.; Klimchuk, O.; Marcou, G.; Tsivadze, A.; 223. Ellis, R. J.; Chartes, J.; Sole, K. C.; Simmance, T. G.; Tong, C. C.; White, F. J.;
Solov’ev, V. Radiochimica Acta 2008, 96, 505–511. Schröder, M.; Tasker, P. A. Chem. Commun. 2009, 583–585.
201. Ali, Sk.M.; Maity, D. K.; De, S.; Shenoi, M. R. K. Desalination 2008, 232, 181–190. 224. Lin, T.; Gasperov, V.; Smith, K. J.; Tong, C. C.; Tasker, P. A. Dalton Trans. 2010,
202. Nagappayya, S. K.; Gaikar, V. G.; Ali, S. M. Desalination Water Treat. 2012, 39, 9760–9762.
38, 1–7. 225. Hill, C. Ion Ex. Solv. Extr. 2010, 19, 119–193.
203. Valente, M.; Sousa, S. F.; Magalhaes, A. L.; Freire, C. J. Mol. Struct: THEOCHEM 226. Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Drew, M. G. B.; Desreux, J. F.;
2010, 946, 77–82. Vidick, G.; Bouslimani, N.; Modolo, G.; Wilden, A.; Sypula, M.; Vu, T.-H.;
204. Varnek, A. In Solvent Extraction: Fundamentals to Industrial Applications, Simonin, J.-P. J. Am. Chem. Soc. 2011, 133, 13093–13102.
Proceedings of ISEC 2008 International Solvent Extraction Conference, Tucson, 227. Lewis, F. W.; Harwood, L. M.; Hudson, M. J.; Distler, P.; John, J.;
2008; 2, 1023–1028 Stamberg, K.; Núñez, A.; Galán, H.; Espartero, A. G. Eur. J. Org. Chem. 2012,
205. Marcos, P. M.; Ascenso, J. R.; Segurado, M. A. P.; Bernardino, R. J.; Cragg, P. J. 1509–1519.
Tetrahedron 2009, 65, 496–503. 228. Sun, X.; Bell, J. R.; Luo, H.; Dai, S. Dalton Trans. 2011, 40, 8019–8023.
206. Yin, X.; Opara, A.; Du, H.; Miller, J. D. Hydrometallurgy 2011, 106, 64. 229. Liu, W.; Li, X.; Wen, Y.; Tan, M. Dalton Trans. 2004, 640–644.
207. Forgan, R. S.; Roach, B. D.; Wood, P. A.; White, F. J.; Campbell, J.; 230. Matloka, K.; Sah, A. K.; Peters, M. W.; Srinivasan, P.; Gelis, A. V.; Regalbuto, M.;
Henderson, D. K.; Kamenetzky, E.; McAllister, F. E.; Parsons, S.; Pidcock, E.; Scott, M. J. Inorg. Chem. 2007, 46,
Richardson, P.; Swart, R. M.; Tasker, P. A. Inorg. Chem. 2011, 50, 4515–4522. 10549–10563.
208. Black, D.; Blake, A. J.; Finn, R. L.; Lindoy, L. F.; Nezhadali, A.; Rougnaghi, G.; 231. Arroyo, F.; Fernández-Pereira, C. Ind. Eng. Chem. Res. 2008, 47,
Tasker, P. A.; Schröder, M. Chem. Commun. 2002, 340–341. 3186–3191.
209. Gordon, R. J.; Campbell, J.; Henderson, D. K.; Henry, D. C. R.; Swart, R. M.; 232. Arroyo, F.; Fernández-Pereira, C.; Olivares, J.; Coca, P. Ind. Eng. Chem. Res.
Tasker, P. A.; White, F. J.; Wood, J. L.; Yellowlees, L. J. Chem. Commun. 2008, 2009, 48, 3573–3579.
4801–4803. 233. Virolainen, S.; Ibana, D.; Paatero, E. Hydrometallurgy 2011, 107, 56–61.