Current Opinion in Solid State and Materials Science 5 (2001) 107–114

Review

Coordination polymers
Stuart R. Batten*
Department of Chemistry, PO Box 23, Monash University, Victoria 3800, Australia

Abstract

The crystal engineering of coordination polymers has always held great potential for applications in many areas, such as molecular
magnetism, heterogeneous catalysis, molecular sieving and non-linear optics. In recent times that potential has been realised, with many
new materials with useful applications reported. In addition, many new interesting network topologies and unusual modes of
interpenetration have been discovered.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Coordination polymers; Crystal engineering

1. Introduction ing lower density, optical transparency and more gentle

synthetic methods. However, magnetic ordering requires
The aim of crystal engineering is to control the way intimate interactions between spin-carrying centres (usually
molecules assemble in the solid state. Since the properties metal centres) within infinite arrays of such centres. A
of any material are largely due to its structure, control over coordination polymer approach allows control over the
the structure allows us to manipulate these properties. The positioning and connectivity of the spin carrying centres,
crystal engineering of coordination polymers has come a and provides the ability to modify successful systems to
long way since its birth 10 years ago [1], however the improve their magnetic properties or incorporate other
principles remain the same. By judicious choice of pre- useful properties.
ferred ligand and metal coordination geometries, control One very successful series of such compounds have
over the topology and geometry of the infinite networks been metal cyanides, most of which possess the Prussian
can be gained. Other, more subtle conditions can also be blue structure. Their cubic structure, however, means that
used to modify structures, such as choice of solvent or no magnetic anisotropy is shown. To circumvent this, the
counterion [2]. Such control allows the deliberate design of heptacyanometalate [Mo(CN) 7 ] 42 , which is not compat-
materials with a range of useful properties, including ible with cubic symmetry, has been used in the construc-
electronic properties, magnetic properties (long-range mag- tion of extended metal cyanide lattices, resulting in mag-
netic ordering, spin-crossover materials), microporosity netically ordering materials which show magnetic aniso-
(including the related properties of ion exchange and tropy [**3].
heterogeneous catalysis), non-linear optical effects and A number of other cyanide-bridged compounds with
luminescent properties. This review will examine such interesting structures, but no magnetic ordering, have also
advances and applications of coordination polymer en- been reported recently. Two such compounds contain
gineering reported in the period 1999–2000. [R 3 Sn(CN) 2 ] 2 bridges. The structure of
[(Ph 3 Sn) 2 Ni(CN) 4 ]?Ph 3 SnOH?solv contains square planar
Ni nodes bridged by [Ph 3 Sn(CN) 2 ] 2 bridges into a NbO-
2. Magnetic ordering in cyanide and dicyanamide like network [4]. Interpenetration is prevented by the
coordination polymers incorporation of Ph 3 SnOH guests, which appear to play a
templation role, and the bulky phenyl groups pendant to
Molecule-based magnetic materials offer a number of the framework. The structure of [CuCN?Me 3 SnCN?pyz],
advantages over traditional inorganic compounds, includ- pyz5pyrazine, however, contains three interpenetrating
diamond networks, with tetrahedral Cu(I) centres bridged
by pyrazine and [Me 3 Sn(CN) 2 ] 2 moieties [5]. A series of
*Tel.: 161-39-905-4606; fax: 161-39-905-4597. compounds synthesised from the reaction of
E-mail address: [email protected] (S.R. Batten). [Re 6 Q 8 (CN) 6 ] 42 , Q5S, Se clusters with metal ions have

1359-0286 / 01 / $ – see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S1359-0286( 00 )00031-0
108 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114

been reported [**6]. The cyanide moieties bridge between the coordination polymers of the dicyanamide (dca,
clusters and metal ions to give 2D and 3D networks. The N(CN) 2 2 ) ligand. The a-[M(dca) 2 ] compounds all have
colour of two of these compounds is reported to change rutile-like structures (Fig. 1) in which octahedral metal
with exposure to various chemical vapours. For example, centres are bridged by three-connecting dca ligands (which
the colour of one compound changes from orange to an coordinate through all three nitrogen atoms). Despite their
intense blue–violet on exposure to diethyl ether vapour. isomorphous structures, the magnetic properties vary wide-
The recent discovery [**7–9] of a new class of magneti- ly: Cr, Mn and Fe are spin-canted antiferromagnets (T N 5
cally ordering compounds has sparked a surge in interest in 47, 16, 19 K), Co and Ni are ferromagnets (T c 59, 20 K),

Fig. 1. Four related structures of dca (dicyanamide, N(CN) 2 2

2 ) and tcm (tricyanomethanide, C(CN) 3 ): (a) the rutile-related network in a-M(dca) 2 [**7–9];
(b) the two interpenetrating rutile-related nets in M(tcm) 2 [15]; (c) the self-penetrating network in M(dca)(tcm) [**52]; (d) the tube-like 1D network in
M(dca) 2 (apym), apym52-aminopyrimidine [**12].
 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114 109

and Cu is a paramagnet. The b-[M(dca) 2 ] phase is formed potential for greater control over pore size and shape. Until
by tetrahedral metals [10], and is composed of (4,4) 2D recently, however, the usefulness of such materials was
sheets of metals bridged by m 2 ligands (the amide nitrogen limited by the loss of crystallinity of such materials after
does not coordinate). The effect of structure on magnetic removal of guest solvent molecules from the lattice, which
properties is illustrated by the fact that both phases can be was interpreted as a collapse of the porous framework.
isolated for M5Co, however while the a phase is a Recent work has reported a number of new coordination
ferromagnet, the b phase is a spin-canted antiferromagnet polymers that retain their porosity, and in some cases
(T N 59 K). The dimensionality of the dicyanamide coordi- remain single crystals, upon removal of solvent.
nation polymers can also be reduced by the introduction of One of the leading researchers in this area has been
terminal solvent ligands such as H 2 O, MeOH, EtOH, DMF Yaghi. He has synthesised a number of interesting such
and pyridine [11]. An unusual tube-like 1D polymer is materials using the polycarboxylate donor ligands bdc
formed when 2-aminopyridine is added to the reaction (1,4-benzenedicarboxylate) and btc (1,3,5-benzenetricar-
mixture [**12]; the topology of the tube is identical to the boxylate) [17–20]. The structure of Tb(bdc)NO 3 has a
square channels in the a-[M(dca) 2 ] rutile-like networks microporous (3,4)-connected net which is capable of
(Fig. 1). reversible molecular sorption and is stable in the absence
Polymorphism and pseudo-polymorphism is common in of guests [17]. The thermal removal of coordinated water
dca coordination polymers. In addition to the a and b molecules from the structure of Tb 2 (bdc) 3 (H 2 O) 4 results
forms of [M(dca) 2 ], a-[Cu(dca) 2 (pyz)] contains two inter- in a microporous structure which also has accessible metal
penetrating a-Po-like 3D networks, while the b form sites which may be used by re-absorbed water or ammonia
contains 2D (4,4) sheets [13]. Two compounds are isolated ligands [18]. Desolvation of Zn 2 (btc)NO 3 ?(EtOH) 5 H 2 O
from a reaction mixture containing Cu(I), dca and 4,49- results in a material in which reabsorption of ethanol
bipyridine whose formulae differ only by the number of vapour occurs in several stages that indicate the coordina-
solvent molecules in the structure; one contains 1D ladder- tively unsaturated zinc centres increase their coordination
like polymers while the other has a thick 2D layer structure number from 3 to 4, 4 to 5, and then 5 to 6 [19]. The most
[*14]. This latter compound displays 2D parallel inter- remarkable compound in this series to date is Zn 4 O(bdc) 3 ?
penetration, with each layer interlocked with four others. (DMF) 8 C 6 H 5 Cl, which is stable in air to 3008C and has a
The mean planes of the layers, however, are parallel but free pore volume of 55–60% [19,20]. The removal of the
not coincident, and thus the interlocking generates an solvent can be achieved without damage to the single
overall 3D structure rather than the usual formation of 2D crystals. The structure consists of an a-Po-like 3D network
layers. Cu(dca)(bpe), bpe51,2-bis(4-pyridyl)ethene also in which Zn 4 O(RCO 2 ) 6 clusters, acting as the six-connect-
has an a phase (two-fold parallel interpenetration of (4,4) ing nodes, are connected by the bridging bdc ligands (Fig.
2D sheets) and a b phase (five interpenetrating diamond 2).
like nets in which the topology of interpenetration is
unprecedented) [*14].
A number of coordination polymers of the related
tricyanomethanide (tcm, C(CN) 2 3 ) ligand have also been
reported. Like their dca analogues, the M(tcm) 2 com-
pounds have rutile like networks, but the larger size of the
ligand results in two interpenetrating networks (Fig. 1)
[15]. An interesting series of compounds are formed by
Cu(I), tcm and either hexamethylenetetramine, 4,49-
bipyridine or 1,2-bis(4-pyridyl)ethene [*16]. All three
compounds have topologically identical 2D (4,4) sheets
but display different methods of maximising packing
efficiency in the structure: interdigitation, interpenetration
and intercalation, respectively.

3. Microporous materials

One of the most promising applications of coordination

polymer design is the synthesis of microporous materials.
Coordination polymers offer a number of advantages over Fig. 2. The structure of the porous Zn 4 O(bdc) 3 , bdc51,4-benzenedicar-
their inorganic rivals (such as zeolites), including unusual boxylate coordination polymer; the central sphere highlights the cavity
pore shapes, more gentle synthetic techniques and the size [19,20].
110 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114

A number of other groups have reported open-network

coordination polymers [21–27]. Porphyrin-based materials
have recently produced a number of such materials [22–
24]. Incorporation of freebase porphyrins into the network
has been shown to produce a solid which will absorb metal
cations from solution [*24]. Kitagawa has demonstrated
very significant methane gas absorption for a number of
porous coordination polymers [25,26].
One very interesting family of coordination polymers
have shown that framework ligands can be modified
through the introduction of side chains without changing
the structure of the material formed [**27]. This allows the
size and chemical environment of the cavities and channels
in the structure to be modified, and illustrates the power of
the coordination polymer approach to microporous materi-
als. Indeed, reaction is observed between a porous host
with pendant alcohol functionality and the vapour of an
acid anhydride, to give a new solid with ester functionality.
Such post framework-assembly chemical transformations
are also seen in another recently reported compound,
which consists of 1D helical chains [*28]. Dehydration
results in cross-linking of these chains (directed by N–H???
O hydrogen bonding) to give a 3D chiral structure which,
oddly enough, can be recrystallised from water without
reformation of the hydrated precursor. Such post assembly
chemistry inevitably leads to the question of catalytic
activity, which has been observed recently in a porous,
homochiral coordination polymer [**29]. This material
Fig. 3. A single acentric diamondoid network of Zn(4-pyridinecarboxy-
displays enantioselective inclusion of metal complexes, late) 2 ligand; three such networks interpenetrate [*35].
and catalyses a transesterification reaction in an enan-
tioselective manner.
5. Interpenetrating networks

The attempted design and synthesis of open structures

often results in the formation of multiple interpenetrating
4. Chiral and non-linear optically active networks networks [**38]. Contrary to expectation, however, inter-
penetration does not prevent the formation of microporous
The production of materials that have second-order non- solids. For example, a recent series of microporous materi-
linear optical (NLO) activity is an area of great interest to als have multiply interpenetrating homochiral (10,3)-a
the crystal engineering community. Such NLO activity, networks [*39]. Another recent porous structure has two
however, requires non-centrosymmetric crystal structures. interpenetrating a-Po networks; despite the porosity, inter-
Chiral networks are similarly desirable. Thus, control over penetration of further networks is prevented by the size of
the crystal packing is required for the successful design of clusters which act as the nodes [*40]. Interpenetration is
such materials. Fortunately, acentric and chiral networks, also of great intrinsic structural interest, and some of the
even when assembled from centrosymmetric, achiral com- more interesting recent systems are detailed here.
ponents, are an increasingly regular outcome for coordina- The ligand sebaconitrile (sebn, 1,10-decanedinitrile)
tion polymers [30–33]. Lin has employed a particularly gives several different structures with interpenetrating
successful method of using unsymmetric ligands which frameworks, of general formula [Ag(sebn) 2 ] 1 , whose
have a pyridyl donor group at one end and a carboxylate structures depend on the counteranion used [*41]. For BF 2 4
donor group at the other (Fig. 3) [34–36]. The materials and ClO 24 , eight interpenetrating diamondoid networks are
produced are up to 10 times better than the standard formed. For PF 2 2
6 and AsF 6 , four interpenetrating SrAl 2 -
potassium dihydrogen phosphate (KDP), and combine related 3D networks are formed.
other useful properties such as insolubility in common The most unusual, however, are the interpenetrating 2D
solvents, transparency in the visible region, and high layers formed with SbF 2 2
6 and CF 3 SO 3 . Interpenetration of
thermal stability. Lin has also reported a related series of 2D networks occurs in two basic forms [**38]. Inclined
lanthanide polymers that, while being centrosymmetric, are 2D interpenetration occurs when the mean planes of any
highly luminescent [37]. two interpenetrating sheets are inclined to each other (i.e.
 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114 111

non-parallel). For example, recent host–guest structures

have been interpreted as inclined interpenetration of (4,4)
covalent networks (M(4,49-bipyridine) 2 (NO 3 ) 2 sheets) and
(6,3) non-covalent networks (aromatic guests connected by
supramolecular interactions) [42]. Another noteworthy
recent structure shows the first instance of interpenetration
of three different inclined sets of planes (which in this case
are mutually perpendicular) (Fig. 4) [*43]. Parallel 2D
interpenetration occurs when the mean planes of any two
interpenetrating sheets are parallel. Usually the mean
planes are also coincident, which results in the formation
of discrete layers of interpenetrating sheets. In the cases of
[Ag(sebn) 2 ](X), X5SbF 2 2
6 , CF 3 SO 3 , which have iso-
morphous structures, the mean planes of the interpenetrat-
ing 2D nets are parallel but not coincident. Each net is
interpenetrated by two others that are offset to it in the
direction perpendicular to the net. As each net is equiva-
lent, these two nets are interpenetrated with two further
offset networks (one each), and so on, resulting in 2D
networks which are infinitely interlocked in the third
dimension, giving an overall 3D structure. A number of
other examples of this new phenomena have been reported
recently [**14,44–46]. In a related example, the first
occurrence of interpenetration between 1D and 2D net-
works has been reported [**47]. The structure contains
layers of (4,4) sheets interpenetrated in an inclined fashion
with 1D chains (Fig. 5). Another recent structure features
penetration of 2D (4,4) sheets by 1D chains in a parallel
fashion [48], however the chains themselves are not Fig. 5. Interpenetrating 1D chains and 2D sheets reported for a Cu
coordination polymer of 1,3-bis(4-pyridyl)propane [**47].

penetrated by the sheets, and thus does not constitute an

interpenetrating system.
The interpenetration of frameworks does present chal-
lenges in the interpretation of structures, and occasionally
the presence of such phenomena is not commented upon
[49–51]. For example, the recently reported structure of
Cu(pyrazine)[Au(CN) 2 ] 2 is described as 1D Cu(pyz)
chains (Cu–N52.06(1) A) ˚ with pendant, terminal
2 ˚ completing the square
Au(CN) 2 rods (Cu–N51.96(1) A)
planar geometry of the copper(II) cations [49]. These
chains are then extensively interdigitated, encouraged by
interchain Au???Au interactions. The report, however,
ignores interchain contacts between the copper atoms and
the ‘terminal’ nitriles of the Au(CN) 22 pendants (Cu–N5
˚ Such contacts give the copper atoms classic
2.43 A).
Jahn–Teller distorted 412 geometry, and the structure can
now be described in terms of two interpenetrating a-Po
networks (Fig. 6).

6. Self-penetration

While interpenetrating networks can be viewed as

Fig. 4. Inclined interpenetration of three different sets of 2D sheets in the polymeric equivalents of molecular catenanes and rotax-
structure of Pt(HL) 2 L 2 ?2H 2 O, L54-pyridinecarboxylate [*43]. anes, the polymeric equivalent of a molecular knot is a
112 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114

have been reported. Zubieta has shown that the use of

common coordination polymer ligands results in formation
of novel new metal–oxide–ligand structures [56–58].
Munakata has used polyaromatic hydrocarbons to bridge
silver atoms into a variety of new network structures
[59–61].

8. Conclusions

The crystal engineering of coordination polymers has

experienced exponential growth in its 10-year history. The
design strategies are now producing molecular magnets,
microporous solids, heterogeneous catalysts and materials
that show NLO activity. Compounds with fascinating
topologies and intricate interweaving of multiple networks
have been discovered. Complete control over the materials
is sometimes elusive, and surprises are often. However, as
Fig. 6. Two interpenetrating a-Po-like nets in the structure of our understanding increases of the numerous factors
Cu(pyrazine)[Au(CN) 2 ] 2 [49]. involved, including the subtle effects of solvent, guest
molecules, counterions and crystallising conditions, more
self-penetrating network [**52,**53,**54,*55]. These are and more will the exciting potential of this area be realised.
single networks that nonetheless contain regions in which
rods penetrate rings in a similar fashion to interpenetrating
nets. Importantly, the rods must penetrate through the References
topological smallest rings of the network. The smallest
rings in a topological sense are the smallest rings possible Papers of particular interest, published within the annual
when leaving a chosen node along one link and returning period of review, have been highlighted as:
via another. Thus, all ‘smallest rings’ are not necessarily * of special interest;
the same size. ** of outstanding interest.
To illustrate, consider the structure of M(dca)(tcm)
[**52]. As mentioned earlier, both a-M(dca) 2 and M(tcm) 2 [1] Hoskins BF, Robson R. Design and construction of a new class of
scaffolding-like materials comprising infinite polymeric frameworks
have rutile-like networks, although the second series have of 3D-linked molecular rods. A reappraisal of the Zn(CN) 2 and
two interpenetrating networks due to the larger size of the Cd(CN) 2 structures and the synthesis and structure of the diamond-
I II I
tcm ligand. If both ligands are combined in the one related frameworks [N(CH 3 ) 4 ][Cu Zn (CN) 4 ] and Cu [4,49,40,4--
structure, a structural compromise is reached – a single, tetracyano-tetraphenylmethane]BF 4 ?xC 6 H 5 NO 2 . J Am Chem Soc
1990;112:1546–54.
self-penetrating network which is closely related to (but [2] Wu H-P, Janiak C, Rheinwald G, Lang H. 5,59-Dicyano-2,29-
different from) the rutile prototype (Fig. 1). There are two bipyridine silver complexes: discrete units or co-ordination polymers
different sorts of nodes in this structure – three-connecting through a chelating and / or bridging metal–ligand interaction. J
nodes (ligands) and six-connecting nodes (metals). From Chem Soc Dalton Trans 1999:183–190.
[**3] Kahn O, Larionova J, Ouahab L. Magnetic anisotropy in cyano-
the three-connecting nodes (the dca and tcm ligands are
bridged bimetallic ferromagnets synthesized from the [Mo(CN) 7 ] 42
topologically indistinguishable) there are three different precursor. Chem Commun 1999:945–952. Review describing use of
possible pairs of links from the node, and thus there are the novel [Mo(CN) 7 ] 42 precursor in formation of networks display-
three different smallest circuits – one four-membered and ing magnetic anisotropy.
two six-membered rings. For the six-connecting node, [4] Niu T, Wang X, Jacobson AJ. A three-dimensional coordination
polymer with an expanded NbO structure. Angew Chem Int Ed
there are fifteen smallest circuits – two four-membered, 1999;38:1934–7.
ten six-membered and three eight-membered rings, which [5] Siebel E, Ibrahim AMA, Fischer RD. [CuCN?Me 3 SnCN?C 4 H 4 N 2 ]: a
means that the Schlafli ¨ symbol for the network is threefold interpenetrating, distorted-diamond framework (C 4 H 4 N 2 5
(4 2 6 10 8 3 )(4 1 6 2 ), the same as the rutile network. The pyrazine). Inorg Chem 1999;38:2530–2.
smallest circuits of the network are thus four-, six- and [**6] Beauvais LG, Shores MP, Long JR. Cyano-bridged Re 6 Q 8 (Q5S,
Se) cluster–cobalt(II) framework materials: versatile solid chemical
eight-membered rings; the self-penetration occurs such that sensors. J Am Chem Soc 2000;122:2763–72. Describes formation of
rods pass through six-membered rings. networks based on cyano-bridged clusters. A number of these
compounds act as sensors for chemical vapours.
[**7] Batten SR, Jensen P, Moubaraki B, Murray KS, Robson R. Structure
and molecular magnetism of the rutile-related compounds M(dca) 2 ,
7. Other developments M5Co II , Ni II , Cu II , dca5dicyanamide, N(CN) 2 2 . Chem Commun
1998:439–440. First report of the structures and magnetic ordering
Finally, two novel approaches to network formation of the M(dca) 2 series of compounds.
 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114 113

[8] Kurmoo M, Kepert CJ. Hard magnets based on transition metal [*24] Sharma CVK, Broker GA, Huddleston JG, Baldwin JW, Metzger
complexes with the dicyanamide anion, hN(CN) 2 j 2 . New J Chem RM, Rogers RD. Design strategies for solid-state supramolecular
1998;22:1515–24. arrays containing both mixed-metalated and freebase porphyrins. J
[9] Manson JL, Kmety CR, Huang Q, Lynn JW, Bendele GM, Pagola S, Am Chem Soc 1999;121:1137–44. Coordination polymers based on
Stephens PW, Liable-Sands LM, Rheingold AL, Epstein AJ, Miller freebase porphyrins show heterogeneous absorption of metal ions
JS. Structure and magnetic ordering of M II [N(CN) 2 ] 2 (M5Co, Ni). from solution.
Chem Mater 1998;10:2552–60. [25] Kondo M, Okubo T, Asami A, Noro S, Yoshitomi T, Kitagawa S,
[10] Jensen P, Batten SR, Fallon GD, Moubaraki B, Murray KS, Price Ishii T, Matsuzaka H, Seki K. Rational synthesis of stable channel-
DJ. Structural isomers of M(dca) 2 molecule-based magnets. Crystal like cavities with methane gas adsorption properties:
structure of tetrahedrally coordinated sheet-like b-Zn(dca) 2 and [hCu 2 (pzdc) 2 (L)j n ] (pzdc5pyrazine-2,3-dicarboxylate; L5a pillar
b-Co / Zn(dca) 2 , and the octahedrally coordinated rutile-like a- ligand). Angew Chem Int Ed 1999;38:140–3.
2 2
Co(dca) 2 , where dca 5dicyanamide, N(CN) 2 , and magnetism of [**26] Noro S, Kitagawa S, Kondo M, Seki K. A new, methane adsorbent,
b-Co(dca) 2 . Chem Commun 1999:177–178. porous coordination polymer [hCuSiF 6 (4,49-bipyridine) 2 j n ]. Angew
[11] Batten SR, Jensen P, Kepert CJ, Kurmoo M, Moubaraki B, Murray Chem Int Ed 2000;39:2082–4. Describes a porous coordination
KS, Price DJ. Syntheses, structures and magnetism of a-Mn(dca) 2 , polymer which shows greater absorption of methane than even the
Mn(dca) 2 (H 2 O) 2 ?H 2 O, Mn(dca) 2 (C 2 H 5 OH) 2 ?(CH 3 ) 2 CO, best zeolite currently known.
Fe(dca) 2 (CH 3 OH) 2 and Mn(dca) 2 (L) 2 , where L5pyridine, CH 3 OH, [**27] Kiang Y-H, Gardner GB, Lee S, Zu Z, Lobkovsky EB. Variable pore
2 2
DMF and dca 5dicyanamide, N(CN) 2 . J Chem Soc Dalton Trans size, variable chemical functionality, and an example of reactivity
1999:2987–2997. within porous phenylacetylene silver salts. J Am Chem Soc
[**12] Jensen P, Batten SR, Moubaraki B, Murray KS. Infinite molecular 1999;121:8204–15. Describes a clever piece of crystal engineering
tubes: structure and magnetism of M(dca) 2 (apym), M5Co, Ni, in which side chains with varying size and functionality are added to
2
apym52-aminopyrimidine, dca5dicyanamide, N(CN) 2 . Chem the framework forming ligands without affecting the topology of the
Commun 2000:793–794. Describes the structures and magnetic framework formed. Thus the size and chemical environment of the
properties of novel tube-like 1D coordination polymers. cavities and channels can be manipulated.
[13] Jensen P, Batten SR, Fallon GD, Hockless DCR, Moubaraki B, [*28] Ranford JD, Vittal JJ, Wu D, Yang X. Thermal conversion of a
Murray KS, Robson R. Synthesis, structural isomerism and magnet- helical coil into a three-dimensional chiral framework. Angew Chem
ism of extended framework compounds of type [Cu(dca) 2 (pyz)] n , Int Ed 1999;38:3498–501. Dehydration of a compound composed of
2
where dca5dicyanamide (N(CN) 2 ) and pyz5pyrazine. J Solid 1D helices results in formation of a chiral 3D network; the process
State Chem 1999;145:387–93. is guided by N–H???O hydrogen bonds in the former structure.
[*14] Batten SR, Harris AR, Jensen P, Murray KS, Ziebell A. Copper(I) [**29] Seo JS, Whang D, Lee H, Jun SI, Oh J, Jeon YJ, Kim K. A
dicyanamide coordination polymers: ladders, sheets, layers, homochiral metal–organic porous material for enantioselective
diamond-like networks and unusual interpenetration. J Chem Soc separation and catalysis. Nature 2000;404:982–6. Describes a chiral
Dalton Trans 2001: in press. A series of related coordination coordination polymer which shows size and enantioselective cata-
polymers which include novel interpenetration motifs. lytic and inclusion properties.
[15] Batten SR, Hoskins BF, Moubaraki B, Murray KS, Robson R. [30] Biradha K, Seward C, Zaworotko MJ. Helical coordination poly-
Crystal structures and magnetic properties of the interpenetrating mers with large chiral cavities. Angew Chem Int Ed 1999;38:492–5.
rutile-related compounds M(tcm) 2 [M5octahedral, divalent metal; [31] Ezuhara T, Endo K, Aoyama Y. Helical coordination polymers from
tcm 2 5tricyanomethanide, C(CN) 2 3 ] and the sheet structures of achiral components in crystals, homochiral crystallization, homo-
[M(tcm) 2 (EtOH) 2 ] (M5Co or Ni). J Chem Soc Dalton Trans chiral helix winding in the solid state, and chirality control by
1999:2977–2986. seeding. J Am Chem Soc 1999;121:3279–83.
[*16] Batten SR, Hoskins BF, Robson R. Interdigitation, interpenetration [32] Barnett SA, Blake AJ, Champness NR, Wilson C. An unusual
and intercalation in layered cuprous tricyanomethanide derivatives. (CuSCN) ` structural motif in the non-centrosymmetric coordination
Chem Eur J 2000;6:156–61. Three closely related compounds with polymer [(CuSCN) 2 (pyrimidine)] ` . Cryst Eng Comm 2000:5.
topologically equivalent networks show three different techniques [*33] Blake AJ, Champness NR, Cooke PA, Nicolson JEB. Synthesis of a
for maximising packing efficiency. chiral adamantoid network–the role of solvent in the construction of
[17] Reineke TM, Eddaoudi M, O’Keeffe M, Yaghi OM. A microporous new coordination networks with silver(I). Chem Commun
lanthanide–organic framework. Angew Chem Int Ed 1999;38:2590– 2000:665–666. Clever ligand design allows the formation of a chiral
4. diamondoid network despite the fact that the diamond prototype is
[18] Reineke TM, Eddaoudi M, Fehr M, Kelley D, Yaghi OM. From achiral.
condensed lanthanide coordination solids to microporous [34] Evans OR, Wang Z, Lin W. An unprecedented 3D coordination
frameworks having accessible metal sites. J Am Chem Soc network composed of two intersecting helices. Chem Commun
1999;121:1651–7. 1999:1903–1904.
[19] Eddaoudi M, Li H, Yaghi OM. Highly porous and stable metal– [*35] Evans OR, Xiong R-G, Wang Z, Wong GK, Lin W. Crystal
organic frameworks: structure design and sorption properties. J Am engineering of acentric diamondoid metal–organic coordination
Chem Soc 2000;122:1391–7. networks. Angew Chem Int Ed 1999;38:536–8. Design of acentric
[**20] Li H, Eddaoudi M, O’Keeffe M, Yaghi OM. Design and synthesis of materials for NLO applications through use of unsymmetric ligands
an exceptionally stable and highly porous metal–organic framework. and formation of odd numbers of interpenetrating networks.
Nature 1999;402:276–9. An exceptionally porous and stable frame- [*36] Lin W, Wang Z, Ma L. A novel octupolar metal–organic NLO
work. material based on a chiral 2D coordination network. J Am Chem
[21] Goodgame DML, Grachvogel DA, Williams DJ. A new type of Soc 1999;121:11249–50. Describes a coordination polymer with
metal–organic large-pore zeotype. Angew Chem Int Ed NLO properties significantly better than the standard KDP.
1999;38:153–6. [37] Ma L, Evans OR, Foxman BM, Lin W. Luminescent lanthanide
[22] Diskin-Posner Y, Dahal S, Goldberg I. Crystal engineering of coordination polymers. Inorg Chem 1999;38:5837–40.
metalloporphyrin zeolite analogues. Angew Chem Int Ed [**38] Batten SR, Robson R. Interpenetrating nets: ordered, periodic
2000;39:1288–92. entanglement. Angew Chem Int Ed 1998;37:1460–94. A com-
[23] Lin K-J. SMTP-1: the first functionalized metalloporphyrin molecu- prehensive review of interpenetrating networks. A continually
lar sieves with large channels. Angew Chem Int Ed 1999;38:2730– updated list of all known interpenetrating frameworks may be
2. obtained from the author (SRB).
 114 S.R. Batten / Current Opinion in Solid State and Materials Science 5 (2001) 107 – 114

[*39] Kepert CJ, Prior TJ, Rosseinsky MJ. A versatile family of inter- [*50] Kuhlman R, Schimek GL, Kolis JW. Inorganic–organic composites
convertible microporous chiral molecular frameworks: the first from solvothermal routes: Extended structures of [CuX(pyrazine)] `
example of ligand control of network chirality. J Am Chem Soc (X5CN, Cl, CF 3 CO 2 ), and Cu(NO 2 ) 2 (pyz). Polyhedron
2000;122:5158–68. Describes formation of compounds containing 1999;18:1379–87. No comment is made of the fact that the structure
two or four homochiral interpenetrating (10,3)-a networks which are of Cu(CN)(pyz) contains two interpenetrating diamondoid networks.
nonetheless microporous. Chirality of the frameworks can be [*51] Choe W, Kiang Y-H, Xu Z, Lee S. Coordination networks of C3 v and
controlled by the chirality of a diol template. C2 v phenylacetylene nitriles and silver(I) salts: interplay of ligand
[*40] Reineke TM, Eddaoudi M, Moler D, O’Keeffe M, Yaghi OM. Large symmetry and molecular dipole moments in the solid state. Chem
free volume in maximally interpenetrating networks: the role of Mater 1999;11:1776–83. The structure of complex 10 actually
secondary building units exemplified by Tb 2 (ADB) 3 [(CH 3 ) 2 SO] 4 ? contains four interpenetrating (10,3)-b networks.
16(CH 3 ) 2 SO. J Am Chem Soc 2000;122:4843–4. Twofold inter- [**52] Jensen P, Price DJ, Batten SR, Moubaraki B, Murray KS. Self-
penetration of a-Po-like networks fails to prevent the formation of a penetration – a structural compromise between single networks and
highly porous structure. interpenetration: magnetic properties and crystal structures of
[*41] Carlucci L, Ciani G, Macchi P, Proserpio DM, Rizzato S. Complex [Mn(dca) 2 (H 2 O)] and [M(dca)(tcm)], M5Co, Ni, Cu, dca5
interwoven polymeric frames from the self-assembly of silver(I) dicyanamide, N(CN) 2 2
2 , tcm5tricyanomethanide, C(CN) 3 . Chem
cations and sebaconitrile. Chem Eur J 1999;5:237–43. Variation of Eur J 2000;6:3186–95. Describes a novel example of crystal
network topology upon variation of counterion, with eightfold engineering in which a series of new structures ([M(dca)(tcm]) are
interpenetrating diamondoid networks, interpenetrating SrAl 2 -like successfully predicted through replacement of the dca.H 2 O motif in
networks, and unusual 2D parallel interpenetration being among the [Mn(dca) 2 (H 2 O)] with the identical (with respect to topology and
motifs observed. size) tcm ligand. The networks are self-penetrating and magnetically
[42] Biradha K, Domasevitch KV, Hogg C, Moulton B, Power KN, ordered at low temperature (except [Cu(dca)(tcm)]).
Zaworotko MJ. Interpenetrating covalent and noncovalent nets in the [**53] Abrahams BF, Batten SR, Grannas MJ, Hamit H, Hoskins BF,
crystal structures of [M(4,49-bipyridine) 2 (NO 3 ) 2 ]?3C 10 H 8 (M5Co, Robson R. Ni(tpt)(NO 3 ) 2 – a three-dimensional network with the
Ni. Cryst Eng 1999;2:37–45. exceptional (12,3) topology: a self-entangled single net. Angew
[*43] Aakeroy¨ CB, Beatty AM, Leinen DS. A versatile route to porous Chem Int Ed 1999;38:1475–7. Describes the first chemical example
solids: Organic–inorganic hybrid materials assembled through hy- of a (12,3) net, and introduces the necessary conditions for a
drogen bonds. Angew Chem Int Ed 1999;38:1815–9. The only network to be described as self-penetrating.
example of inclined interpenetration of three mutually perpendicular [**54] Withersby MA, Blake AJ, Champness NR, Cooke PA, Hubberstey P,
stacks of 2D sheets, a mode of interpenetration which was predicted ¨
Schroder M. Assembly of a three-dimensional polyknotted coordina-
in Ref. [**38]. tion polymer. J Am Chem Soc 2000;122:4044–6. A self-penetrating
[44] Tong M-L, Chen X-M, Ye B-H, Ji L-N. Self-assembled three- network based on interpenetrating ladders that are cross-linked into
dimensional coordination polymers with unusual ligand-unsupported a single network by nitrate anions.
Ag–Ag bonds: synthesis, structures, and luminescent properties. [*55] Plater MJ, Foreman MRStJ, Gelbrich T, Hursthouse MB. Synthesis
Angew Chem Int Ed 1999;38:2237–40. and characterisation of infinite di- and tri-nuclear zinc co-ordination
[45] Carlucci L, Ciani G, Proserpio DM, Rizzato S. Chiral packing of networks with flexible dipyridyl ligands. J Chem Soc Dalton Trans
chiral quintuple layers polycatenated to give a three-dimensional 2000:1995–2000. Compound 1 has a self-penetrating network.
network in the coordination polymer [56] Hagrman PJ, Bridges C, Greedan JE, Zubieta J. A three-dimensional
[Co 5 (bpe) 9 (H 2 O) 8 (SO 4 ) 4 ](SO 4 )?14H 2 O [bpe51,2-bis(4- organic–inorganic composite material constructed from copper–
pyridyl)ethane]. Chem Commun 2000:1319–1320. triazolate networks linked through vanadium oxide chains:
[*46] Chesnut DJ, Kusnetzow A, Birge R, Zubieta J. Ligand influences on [hCu 3 (trz) 2 jV4 O 12 ]. J Chem Soc Dalton Trans 1999:2901–2903.
copper cyanide solid-state architecture: flattened and fused ‘slinky’, [57] Hagrman D, Hagrman PJ, Zubieta J. Solid-state coordination
corrugated sheet, and ribbon motifs in the copper–cyanide–triazo- chemistry: the self-assembly of microporous organic–inorganic
late–organoamine family. Inorg Chem 1999;38:5485–95. Com- hybrid frameworks constructed from tetrapyridylporphyrin and
pound 1 is composed of 2D layers which interpenetrate, although the bimetallic oxide chains or oxide clusters. Angew Chem Int Ed
interpenetration is incorrectly assigned as inclined interpenetration. 1999;38:3165–8.
The interpenetration is in fact parallel interpenetration, with each [**58] Hagrman PJ, Hagrman D, Zubieta J. Organic–inorganic hybrid
layer interlocked with two others whose mean planes are parallel but materials: from ‘simple’ coordination polymers to organodiamine-
not coincident; an overall 3D structure thus results. Each layer is templated molybdenum oxides. Angew Chem Int Ed 1999;38:2638–
also interdigitated with two others. 84. An excellent review of the authors’ metal oxide work, and of
[**47] Carlucci L, Ciani G, Moret M, Proserpio DM, Rizzato S. Polymeric coordination polymers in general.
layers catenated by ribbons of rings in a three-dimensional self- [59] Munakata M, Wu LP, Ning GL, Kuroda-Sowa T, Maekawa M,
assembled architecture: a nanoporous network with spongelike Suenaga Y, Maeno N. Construction of metal sandwich systems
behaviour. Angew Chem Int Ed 2000;39:1506–10. First example of derived from assembly of silver(I) complexes with polycyclic
interpenetration between 1D networks and 2D networks. aromatic compounds. J Am Chem Soc 1999;121:4968–76.
[48] Sharma CVK, Rogers RD. ‘Molecular Chinese blinds’: self-organi- [60] Ning GL, Wu LP, Sugimoto K, Munakata M, Kuroda-Sowa T,
zation of tetranitrato lanthanide complexes into open, chiral hydro- Maekawa M. Construction of 2-D multilayer structures: silver(I)
gen bonded networks. Chem Commun 1999:83–84. complexes with linear aromatic compounds. J Chem Soc Dalton
[49] Yeung W-F, Wong W-T, Zuo J-L, Lau T-C. Synthesis and structures Trans 1999:2529–2536.
of novel heterobimetallic Cu(II)–Au(I) complexes [61] Munakata M, Wu LP, Sugimoto K, Kuroda-Sowa T, Maekawa M,
Cu(cyclen)[Au(CN) 2 ] 2 and Cu(pyz)[Au(CN) 2 ] 2 . J Chem Soc Dalton Suenaga Y, Maeno N, Fujita M. Silver(I) complex assemblies with
Trans 2000:629–631. non-planar aromatic compounds. Inorg Chem 1999;38:5674–80.