CHAPTER 1

Introduction

1.1 Introduction

Sometime between 1704 and 1705, a Berlin colourmaker named Diesbach madea mistake.1 He was trying to make a red pigment known as cochineal red lake.The recipe was simple – iron sulfate and potash. But it turned out pale. Uponfurther concentration, it became deep blue! By using cheap potash, con-taminated with animal oil made from ox blood, Diesbach had created PrussianBlue. This was the first man-made coordination polymer and in fact the firstman-made coordination compound. It was also a valuable pigment; within afew short years it was being made commercially from a closely guarded recipe.It would, however, be another 372 years before the structure of Prussian

Blue, Fe4[Fe(CN)6]3 � xH2O, would be determined (Figure 1.1a).2 In the inter-vening years, little attention was paid to coordination polymers (certainly muchless than their organic cousins received), with only a few scattered structuralstudies. The structures of Zn(CN)2 and Cd(CN)2 were reported by a Russiangroup in the depths of World War II.3 Powell and Rayner determined thestructures of the Hofmann clathrate, [Ni(NH3)2Ni(CN)4] � 2C6H6, shortlyafterwards (Figure 1.1b);4 this work was later extensively followed up byIwamoto’s group on related compounds.5 In 1959, a Japanese group reported,remarkably, that they had determined that the structure of [Cu(adiponi-trile)]NO3 contained six interpenetrating diamond networks.6 The 1D chainstructures of Ag(pyrazine)NO3 and Cu(pyrazine)(NO3)2 were reported in 1966and 1970, respectively.7,8 The crystal structure of Co(pyrazine)2Cl2 was shownto have a square grid structure in 1971.9

As the 1980s came to a close, there was increasing interest in these materi-als,10 particularly in the field of molecule-based magnetic materials.11 However,it was not until a short communication in 1989,12 and a subsequent full paper in1990,13 that interest really took off.

1

Coordination Polymers: Design, Analysis and Application

By Stuart R. Batten, Suzanne M. Neville and David R. Turner

r Stuart R. Batten, Suzanne M. Neville and David R. Turner, 2009

Published by the Royal Society of Chemistry, www.rsc.org

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Figure 1.1 The structures of (a) Prussian Blue2 and (b) the Hofmann clathrate.4

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In these and subsequent papers,14,15 Robson, Hoskins and co-workers out-lined a net-based approach to the design of coordination polymers. They tookthe landmark work of Wells,16 which described crystal structures in terms ofnetworks, and applied it to the design of new coordination polymers (Figure 1.2).Through this design approach, they proposed that newmaterials with interestingproperties such as porosity and catalysis could be deliberately engineered. Theseideas soon caught on, with other early groups in the field17–23 making importantcontributions that would ultimately lead to the explosion in research illustratedin Figure 1.3.

Figure 1.3 The number of hits for ‘coordination polymer’ or ‘metal–organic frame-work’ in the Science Citation Index, by year.

Figure 1.2 An early framework coordination polymer reported by Hoskins andRobson.13

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1.2 Crystal Engineering, Supramolecular Chemistry,

Metallosupramolecules

The development of coordination polymer research was reinforced by thegrowth of two other closely related areas: crystal engineering and supramole-cular chemistry (particularly metallosupramolecular chemistry).Crystal engineering seeks to understand why molecules pack in the ways that

they do and to use that knowledge to deliberately engineer the arrangements ofmolecules in new materials.24 This is important because the properties ofmaterials are often governed by the way in which their constituent moleculesare arranged. Control over this arrangement gives control over the properties.In ‘molecular’ (largely organic) crystal engineering, the interactions are

weaker than coordination bonds and can range in strength from very stronghydrogen bonding to weak C–H � � �A hydrogen bonds, halogen bonds, pinteractions and, ultimately, van der Waals forces. The crystal engineer seeks tounderstand and harness all these interactions. However, despite the differencesin the interactions, there is much that is common in these two areas. Indeed,coordination polymers, which essentially exist only in the solid state, should beconsidered as a subset of crystal engineering. Furthermore, the net-basedapproach for coordination polymers is equally valid for molecular speciesconnected by well-defined interactions. For example, trimesic acid (benzene-1,3,5-tricarboxylic acid) readily forms hexagonal sheets in which the moleculesare connected by hydrogen bonding, as shown in Figure 1.4a.25 The largeorganic molecule shown in Figure 1.4b assembles, as one would predict, intoseven interpenetrating diamond networks through hydrogen bonding betweenthe peripheral functional groups.26

Many of the concepts and terminology in molecular crystal engineering alsoapply to coordination polymers. Interactions between molecules that directtheir packing arrangements (such as the hydrogen bonding carboxylate dimermotif in Figure 1.4a) are known as supramolecular synthons;27 in coordinationpolymers, the main synthons are coordination bonds (although weaker syn-thons can also be important, as discussed in Chapter 4). The building blocksused to create the structure, such as the molecules shown in Figure 1.4, arecalled tectons;28 for coordination polymers, the tectons are metal ions andligands. These two concepts are highlighted in Figure 1.5.The aim of supramolecular chemistry is similar: to create assemblies of mole-

cules, that is, not to create structures an atom at a time, but to design moleculessuch that when combined they spontaneously self-assemble in a predeterminedfashion into larger architectures.29 Thus crystal engineering can, in fact, beconsidered to be the supramolecular chemistry of the solid state. To quoteDunitz, ‘The crystal is, in a sense, the supramolecule par excellence . . . ’.30

The supramolecular chemist, like the crystal engineer, uses a range non-covalent intermolecular interactions, including hydrogen bonding and coordi-nation bonds. Use of the later gives rise to metallosupramolecular chemistry,and much of the design and indeed the structures obtained have close rela-tionships to coordination polymers. For example, the design and chemistry

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(a)

(b)

Figure 1.4 (a) The hydrogen-bonded sheets formed by trimesic acid24 and (b) a mole-cular tecton which assembles via hydrogen bonding into the diamond net.25

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may be similar, except that the use of a convergent ligand building blockwill give a metallosupramolecule whereas a divergent one will generate apolymer (Figure 1.6a). Alternatively, even the same bridging ligand canbe used, with construction of a metallosupramolecule being directed by the useof ‘capping’ chelating co-ligands on the metals [such as 2,20-bipyridine, ethy-lenediamine (en), 1,10-phenanthroline, 1,4,7-triazacyclononane (TACN),cyclopentadiene]. In the absence of these capping groups, polymers are formed(Figure 1.6b). Despite the different products, both areas have the same modularapproach to the design and synthesis and similar (or even the same) buildingblocks.Even the architectures achieved in the two fields can be similar. The supra-

molecule shown in Figure 1.7a, constructed from 4,40-bipyridine (4,40-bipy) and(en)PdII,31 has the same structure as the windows in the 2D coordinationpolymer obtained from reaction of the same ligand with ZnSiF6 (Figure 1.7b).

32

The molecular cube in Figure 1.7c has the same connectivity as the cavities inPrussian Blue.33 Reaction of 2,4,6-tri(4-pyridyl)-1,3,5-triazine (tpt) with(en)PdII gives the discrete cages shown in Figure 1.7d;34 a similar reaction withCuI generates a 3D polymer which contains the same cages (Figure 1.7e).35 Inthe later structure there are no capping groups on the metal to terminate thestructure and thus a polymer is generated in which the cages are connected byshared metal atoms.

1.3 What is a Coordination Polymer?

A coordination polymer contains metal ions linked by coordinated ligands intoan infinite array. This infinite net must be defined by coordination bonds andthus molecular species linked only by hydrogen bonding, such as the exampleshown in Figure 1.8,36 are elegant instances of molecular crystal engineeringbut are not coordination polymers. Similarly, a structure linked by coordina-tion bonds in one direction and hydrogen bonds it two other directions is a 1Dcoordination polymer (although an overall 3D net may be defined by both setsof interactions).

O

O

O

O H

H H

O

O O

O H O

H O O

O H

NAgNNAg N Ag N N Ag

SynthonsTectons

Figure 1.5 Representative synthons and tectons for both organic hydrogen-bondednets (top) and coordination polymers (bottom).

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We also exclude here more ‘inorganic’ materials, such as halides, oxides,hydroxides, alkoxides, sulfides and polyoxides (sulfates, phosphates, etc.),although we do include pseudohalides such as cyanide, azide and thiocyanate.Furthermore, for the purposes of this book, we largely ignore alkali andalkaline earth metals, which have more ionic bonding, and main group metals,in which the bonding is more covalent, and thus focus largely on the transitionand lanthanoid ions.There are good reasons for doing this. One feature of the design of coordi-

nation polymers is that the strength and lability of the coordination bond aresuch that ordered materials can be readily synthesised because of the reversibilityof these interactions. Unlike covalently bonded organic polymers, in which the

LM

LM

LM

LM

ML

ML

ML

ML

ML

Infinite 3D Polymer

M

Discrete Supramolecular Cube

Bridging Ligand

(a)

(b)

Figure 1.6 Direction of the formation of metallosupramolecules versus coordinationpolymers through use of (a) convergent versus divergent ligands and (b)use of terminal capping ligands.

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Figure 1.7 (a) A molecular square formed from 4,40-bipy and capping en ligands;30

(b) a 2D sheet formed by 4,40-bipy;31 (c) a molecular metal cyanide cubecontaining capping TACN ligands;32 (d) a cage complex constructed withtpt and capping en ligands;33 (e) a coordination polymer containinganalogous cages to part (d) linked through shared metal atoms.34

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bonds are largely irreversible, errors in the assembly of a coordination polymercan be readily corrected during growth so that a periodic 3D structure withcrystallographic order can be achieved. By contrast, in an organic polymermistakes are ‘locked in’ once made, resulting in a material with much less per-iodic ordering. This ordering of coordination polymers allows detailed structuraldetermination through X-ray crystallography and, through this, precise struc-ture–property correlations. It is also important to the properties themselves, e.g.a regularity and consistency of pore size and environment that cannot beachieved with amorphous materials. On the other hand, the coordination bond isalso strong enough to provide robust materials and good electronic and mag-netic communication between metal centres. It is also directional, with generallypredictable geometries around the metal centre (particularly for transitionmetals), allowing design to be attempted with some degree of confidence.A coordination polymer thus consists essentially of metal and ligands,

although they often include guests and counterions. The metal ions, as discussedabove, are usually transition metals and/or lanthanoids. For transition metals,the field is dominated by the first-row elements (plus Zn, Cd, Hg, Ag and, to alesser extent, Au, Pd, Pt), due to their kinetic lability and ready availability andstability. Generally, transition metals have been more popular, due in part to themore predictable nature of their coordination geometries; however, lanthanoidshave attracted increased attention recently, with their higher connectivityleading to interesting topologies, in addition to other inherent properties of

Figure 1.8 A hydrogen-bonded network formed by a coordination complex, and nota coordination polymer.35

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interest (e.g. luminescence). These metals are commonly used as their halide,nitrate, perchlorate, tetrafluoroborate, hexafluorophosphate, hexafluorosilicateor triflate salts; ‘non-coordinating’ anions are usually preferred.Although the nature of metal salt chosen is important, the real variation in

coordination polymers comes through the infinite variability and creativity ofligand design. Nonetheless, there are a number of features that are common tomost ligands used (Figure 1.9). Typically, a ligand might have two divergentcoordination sites (although there are many examples of higher connectivity),and these coordination sites are usually pyridyl, imidazole, nitrile or carbox-ylate functional groups (discounting the large body of pseudohalide work).These ligands can also range from the very rigid to the completely flexible, withthe corresponding loss in predictability.

1.4 Synthetic Techniques

One of the challenges of this research is to obtain single crystals suitablefor detailed crystallographic analysis. Unlike molecular species, mostcoordination polymers are insoluble once synthesised (a property whichis advantageous for other aspects) and so recrystallisation is not an option.If the polymers can be dissolved, it is usually through the use ofstrongly coordinating solvents, which are then likely to become part of therecrystallised species, which therefore becomes a different material to the ori-ginal phase.

R N R NN

R C N R

O

O

NN

NN

Figure 1.9 Features of typical ligands used for coordination polymer construction,including (top) typical donor groups and (bottom) rigid versus flexibleligand choice.

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Crystals are therefore usually obtained directly from the synthetic reactionmixtures. Although some species crystallise nicely from directly mixed solu-tions, for other systems the key to obtaining good crystals is to slow the pre-cipitation down. This is most commonly done by allowing two separatesolutions of metals and ligands to diffuse slowly into each other, and a numberof different techniques have been established to this end (Figure 1.10). Thesimplest method is to layer carefully one solution on top of another in a smallvial or tube. Often a buffer layer of pure solvent is layered between the two andthe use of solvents with different densities (e.g. MeOH versus CHCl3) greatlyaids separation. This layered solution should then be left so that the crystals cangrow; typically this may take in the order of 2 weeks, although crystallisationcan often take much longer (or shorter) times and so the reaction should bechecked regularly, preferably without disturbing the crystal growth throughhandling. Regular inspection is important as crystals can come and go (forkinetic products) or become flawed, overgrown or otherwise deteriorate inquality over time.Other variations on this technique include locking one solution into a gel

through the addition of a gelling agent such as tetramethoxysilane. The gelslows diffusion through reduction of convection and also provides a support forthe growing crystals. Specially designed glassware such as H-tubes and U-tubes

Solution BSolution A

U tube

Solution BSolution A H tube

Solution B

Buffer Layer

Solution A

Solution B

Gel Containing Solution A

Figure 1.10 Various methods for slow growth of coordination polymer crystals.

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(Figure 1.10) can also be used; often these can have a frit in the middle or (in thecase of U-tubes) a separating gel plug can be created at the bottom first.As detailed in Chapter 4, there are a number of factors that contribute to

stable crystalline packing arrangements. For the synthetic chemist, this meansthat there are therefore a number of other variables that can be adjusted toproduce crystals. Variation of solvent, counterion or even metal choice can beexplored, as can synthetic tweaks to the ligands. More recently, the use ofsolvothermal techniques has become increasingly popular, both as a method ofobtaining good single crystals and as a means of obtaining phases which areunavailable through bench-top techniques.There is, overall, a large parameter space which can be explored in the quest

for single crystals. However, one of the key reasons for obtaining crystal struc-tures is to draw relationships between structures and properties and thus gaininsights that can feed into the design of new materials. Therefore, it is importantto recognise that the structures obtained from single crystals may be inherentlyunrepresentative (because the crystallographer chooses the best crystal available,for obvious reasons) of the bulk material upon which the properties are tested.Furthermore, reactions can often give more than one product. Hence it isimportant to check the correlation between the single crystals and the bulkproduct, and this is most easily achieved through the use of techniques such aspowder diffraction or (less convincingly) infrared or Raman spectroscopy.Finally, although we largely focus in this book on materials characterised

through single-crystal crystallography, the structures of some simple coordi-nation polymers have been determined directly through powder diffraction.37

Powder diffraction can also be used to correlated known structures and newmicrocrystalline materials. These latter materials may be analogous to knownstructures but lacking in single crystals (e.g. the same structure but differentmetals) or synthesised using unusual techniques, such as solid-state decom-position or mechanochemical techniques.38 Furthermore, non-crystallinematerials can also have very interesting properties even if the detailed structureis unknown. The compound V(tcne)2 � 0.5CH2Cl2, for example, has shownmagnetic ordering above room temperature.39 This material has unfortunatelyonly ever been obtained as an amorphous powder, so its structure, which is nodoubt key to its magnetism, remains unknown. But it is still a magnet.

1.5 Design, Analysis, Application

The rest of this book broadly follows the themes of design, analysis andapplication. Chapter 2 deals with design (nets), Chapter 3 deals with some of theconsequences of nets (interpenetration) and Chapter 4 examines in detail themany other aspects that should be taken into account when designing orexamining a structure. In the following four chapters, we provide an extensiveanalysis of reported coordination polymers and related areas such as organo-metallic networks and inorganic–organic hybrid materials. Finally, we look atthe application of these materials to a number of fields, including magnetism

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(long-range ordering, spin crossover), porosity (gas storage, ion andguest exchange), non-linear optical activity, chiral networks, reactive networks,heterogeneous catalysis, luminescence, multifunctional materials and otherassorted properties. The examples given throughout have been chosen basedon their ability to illustrate a point, their historical significance or the factthat they are either typical or atypical (even exceptional) of a larger class ofmaterials. In many cases, the choice is purely subjective and readers are directedto a long list of literature reviews available as additional complementaryresources.15,40–96

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