MICROREVIEW

DOI: 10.1002/ejic.200900180

Arene Ruthenium Cages: Boxes Full of Surprises

Bruno Therrien*[a]

Keywords: Arene ligands / Bioinorganic chemistry / Ruthenium / Self-assembly / Supramolecular chemistry

Self-assembly of polypyridyl ligands with dinuclear arene ru- and giving rise to potential drug delivery systems; (iii)
thenium building blocks bridged by chlorido, oxalato or metalla-boxes that can be used to stabilise the formation of
benzoquinonato ligands has allowed the construction of a G-quadruplex DNA. This microreview covers the synthetic
wide range of cationic metalla complexes possessing dif- and structural aspects of these metalla complexes, as well as
ferent architectures and functionalities: (i) metalla-rectangles their most promising applications, with a particular focus on
showing host–guest possibilities and allowing intramolecular their potential biological applications.
template-controlled photochemical [2 + 2] dimerisation reac- (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
tions; (ii) metalla-prisms allowing encapsulation of molecules Germany, 2009)

Introduction lecular boxes have been used to generate confined environ-

ments to encapsulate compounds,[5] to protect or stabilise
Boxes have undoubtedly been made as receptacles for ev- an otherwise too sensitive molecule,[6] to recognise and trap
ery conceivable object. They come in all shapes and sizes specific guest molecules[7] or to act as microreactors for spe-
and can be found everywhere in our everyday lives. They cific reactions.[8]
can be purely aesthetic or have a specific purpose such as In the search for new building blocks for the synthesis of
to protect, hide, support or transport objects, and the ro- supramolecular boxes with comparable properties, there is
bustness of the box will depend on its purpose. With a view an increasing interest in using transition-metal complexes
to performing similar functions, the synthesis of molecular with octahedral geometry.[9] Cotton and co-workers have
boxes has attracted a great deal of interest from synthetic built up two- and three-dimensional architectures from
chemists, and the self-assembly of transition-metal com- metal–metal paddlewheel units.[10] Similarly, the fac-Re-
plexes with polydentate ligands to give discrete supramolec- (CO)3 corner system was judiciously chosen to prepare mo-
ular boxes has been studied by several groups. Pioneered by lecular rectangles[11] or triangular prisms.[12] The tridentate
Fujita in the 1990s,[1] and subsequently developed by ligand 1,4,7-trithiacyclononane, which coordinates facially
others,[2] the combination of 90° coordination building to ruthenium, was used to form a supramolecular cube,[13]
blocks and linear ligands to form square and rectangular while polypyrazolyl chelating ligands coordinated to cobalt,
architectures has been extensively exploited. A few years manganese and zinc were used to generate various polyhe-
later, the same approach was used to generate three-dimen- dral cages.[14] The underlying strategy in those examples im-
sional networks.[3] So far, a multitude of two- and three- plies the blocking of concomitant coordination sites at the
dimensional structures incorporating transition metals with octahedral metal centres, thus generating a preorganised ar-
square-planar geometry have been synthesised.[4] These mo- rangement before the formation of the supramolecular as-
sembly.
[a] Institute of Chemistry, University of Neuchatel, In a similar manner, cyclopentadienyl or arene ligands
Case postale 158, 2009 Neuchatel, Switzerland
Fax: +41-032-7182511 can be used to control the accessibility of coordination sites
E-mail: [email protected] at an octahedral metal centre. The use of these η5 or η6

Born and raised in Canada, Bruno Therrien studied chemistry at the University of Montreal, where he learnt crystallogra-
phy in the group of André Beauchamp. He left Canada to obtain his Ph.D. in 1998 at the University of Bern, Switzerland,
under the supervision of Thomas R. Ward. He undertook several postdoctoral positions (Weizmann Institute, Massey
University, Tokyo University) and currently holds an independent Senior Researcher position at the University of Neu-
chatel. His main research interests are supramolecular assemblies and biological applications of arene ruthenium com-
plexes.

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MICROREVIEW B. Therrien

ligands has its advantages: (i) The aromatic ligand occupies complexes in excellent yield.[20] Indeed, the synthesis of di-
three of the six coordination sites at the metal centre, thus nuclear building blocks is straightforward: Reaction of
limiting the number of available coordination sites and [Ru2(arene)2(µ-Cl)2Cl2] (1) with ammonium oxalate ([NH4]2-
therefore allowing better control for the synthesis of two- [C2O4]) or 1,4-benzoquinone derivatives (2,5-dihydroxy-1,4-
or three-dimensional assemblies. (ii) The strongly bonded benzoquinone = C6H4O4; 2,5-dichloro-1,4-benzoquinone =
aromatic ligand allows different substituents that can en- C6H2Cl2O4) affords the corresponding dinuclear arene ru-
hance the solubility or add new properties to the molecular thenium building blocks with various metal–metal dis-
assembly. In this respect, CpM and Cp*M (M = Rh, Ir; Cp tances: [Ru2(arene)2(µ-C2O4)Cl2] (2), [Ru2(arene)2(µ-
= C5H5; Cp* = C5Me5) units have been extensively used to C6H2O4)Cl2] (3) and [Ru2(arene)2(µ-C6Cl2O4)Cl2] (4),
generate metalla-cycles, -rectangles, -prisms and other sup- which are shown in Figure 2.
ramolecular assemblies.[15] To a lesser extent, arene ruthe-
nium complexes (arene = C6H6, C6H5Me, p-iPrC6H4Me,
C6Me6) were utilised to build up similar supramolecular as-
semblies with diverse functionalities and properties. By
using tridentate ligands with various functionalities and co-
ordinating abilities, a series of neutral and cationic tri-, tet-
ra- and hexanuclear metalla-cycles have been synthesised[16]
(see Figure 1). With flexible spacers which connect two tri-
functional units, expanded helicates with six arene ruthe-
nium moieties have been obtained.[17] In some cases, these
systems are capable of binding small molecules with great
specificity; therefore, applications as sensors have been
sought for these metalla complexes. Reviews dealing with
these supramolecular architectures incorporating half-sand-
wich complexes with polyfunctional ligands have been pub-
lished in recent years.[18]

Figure 2. Dinuclear arene ruthenium building blocks.

The dinuclear clips 2, 3 and 4 can further react with two

equivalents of AgCF3SO3 to generate, after removal of
AgCl, the coordinatively unsaturated moieties [Ru2(arene)2-
(µ-C2O4)]2+ (2⬘), [Ru2(arene)2(µ-C6H2O4)]2+ (3⬘) and [Ru2-
(arene)2(µ-C6Cl2O4)]2+ (4⬘), respectively. These intermediate
moieties are occasionally isolated as solvated species, for
example the reaction of 2b in methanol with AgCF3SO3 for
which the dicationic methanol derivative [Ru2(p-
Figure 1. Examples of tri-[16c] and hexanuclear[16f] metalla-cycles. iPrC6H4Me)2(CH3OH)2(µ-C2O4)]2+ was isolated and fully
characterised (see Scheme 1).[21] The X-ray structural analy-
Recently we have used arene ruthenium complexes as sis of [Ru2(p-iPrC6H4Me)2(CH3OH)2(µ-C2O4)](CF3SO3)2
building blocks for the assembly of a series of cationic reveals an anti geometry of the two coordinated methanol
metalla-rectangles, cationic triangular metalla-prisms and molecules. However, it is worth mentioning that, to form
cationic metalla-boxes containing bridging chlorido (Cl–), discrete supramolecular assemblies, a syn geometry of the
oxalato (C2O42–), 2,5-dihydroxy-1,4-benzoquinonato incoming polypyridyl ligands is needed. The removal of the
2–
(C6H2O4 ) and 2,5-dichloro-1,4-benzoquinonato two chlorido ligands, which generates a highly reactive un-
(C6Cl2O42–) ligands and connected by rigid polypyridyl li- saturated clip, is an important feature in the synthesis of
gands. The starting arene ruthenium materials are easily these supramolecular assemblies. It gives opportunities to
prepared in gram scale, they are stable and some are even the preorganised dinuclear clips to react with linear bipyr-
commercially available. The most common method of prep- idyl ligands to form metalla-rectangles, with planar tripyr-
aration of arene ruthenium complexes is the reaction of idyl ligands to form triangular metalla-prisms and with tet-
RuCl3·nH2O with a cyclohexadiene derivative in an EtOH/ rapyridyl porphyrin ligands to form metalla-boxes.
H2O solvent mixture.[19] This simple strategy allows the in- This review intends to give a concise overview of these
troduction of a wide range of η6-arene ligands (a: arene = arene ruthenium assemblies connected with polypyridyl li-
C6H5Me; b: arene = p-iPrC6H4Me; c: arene = C6Me6, see gands with a particular focus on the synthetic methods and
Figure 2). The resulting chlorido-bridged dimers [Ru2(ar- the potential applications for these systems. A special em-
ene)2(µ-Cl)2Cl2] (1) are generally air-stable and can react phasis has been placed on our personal contributions in
with a wide variety of ligands, by cleavage of the chlorido- this field over the last three years, although contributions
bridges, to afford mono- or polynuclear arene ruthenium from other groups are also discussed.

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Arene Ruthenium Cages: Boxes Full of Surprises

tors, pyrazine (prz), 4,4⬘-bipyridine (bpy), 4,4⬘-bipyridyleth-

ylene (bpe) and 4-[5-(4-pyridyl)-1,3,4-oxadiazol-2-yl]pyr-
idine (bpo) to generate the corresponding metalla-rect-
angles [Ru4(p-iPrC6H4Me)4(µ-prz)2(µ-C6Cl2O4)2]4+ (6b),
[Ru4(p-iPrC6H4Me)4(µ-bpy)2(µ-C6Cl2O4)2]4+ (7b), [Ru4(p-
iPrC6H4Me)4(µ-bpe)2(µ-C6Cl2O4)2]4+ (8b) and [Ru4(p-
iPrC6H4Me)4(µ-bpo)2(µ-C6Cl2O4)2]4+ (9b), which are
shown in Figure 3.[23]

Scheme 1. Synthesis of the solvated dinuclear oxalato clip [Ru2(p-

iPrC6H4Me)2(CH3OH)2(µ-C2O4)]2+.[21]

Supramolecular Arene Ruthenium Assemblies

Arene Ruthenium Metalla-Rectangles
The synthesis of various size polygons such as triangles,
squares, pentagons or hexagons has been successfully devel-
oped and used as potential sensors, probes, photonic de-
vices, catalysts and in basic host–guest chemistry.[22] Despite
their relative simplicity, molecular rectangles are more diffi-
cult to obtain than symmetrical polygons. Simultaneous
mixing of two different connector ligands with metal cor-
ners does not favour the formation of the desired rectangle.
Indeed, due to the strong enthalpic driving force, the forma- Figure 3. Molecular structures of metalla-rectangles 6b, 7b, 8b and
tion of two molecular squares is favoured in general. How- 9b.[23]
ever, to overcome this problem, the use of dinuclear arene
ruthenium building blocks shows great potential. Following the same strategy, we recently synthesised two
The first entry in the field of supramolecular assemblies analogous metalla-rectangles: [Ru4(C6Me6)4(µ-bpe)2(µ-
of metalla-rectangles incorporating arene ruthenium com- C6Cl2O4)2]4+ (8c) and [Ru4(C6Me6)4(µ-bpy)2(µ-C6H2O4)2]4+
plexes dates back to 1997:[21] The tetranuclear complex, (10c), shown in Figure 4. X-ray structural analyses of 8c
[Ru4(p-iPrC6H4Me)4(µ-bpy)2(µ-C2O4)2]4+ (5b), a molecular and 10c have been performed.
rectangle in which four arene ruthenium units (arene = p-
iPrC6H4Me) are bridged by two oxalato ligands and two
4,4⬘-bipyridine (bpy) units, was synthesised in methanol
from the dinuclear complex 2b in the presence of
AgCF3SO3 (see Scheme 2). The key aspect in the exclusive
formation of rectangle 5b was a two-step strategy, in which
two preorganised bimetallic units (2⬘b) were connected to-
gether by two rigid bidentate ligands. However, this macro-
cyclic arrangement was too small to accommodate guest
molecules between the two bpy units, the metal–metal dis-
tances being 5.532(9) and 11.315(10).
Figure 4. Metalla-rectangles [Ru4(C6Me6)4(µ-bpe)2(µ-C6Cl2O4)2]4+
(8c) and [Ru4(p-iPrC6H4Me)4(µ-bpy)2(µ-C6H2O4)2]4+ (10c).[24,25]

Interestingly, in the solid state, [10c](CF3SO3)4 forms

one-dimensional channels with Ru–Ru separations of 7.9
and 11.3 Å[24] (see Figure 5). A similar arrangement has
been found in the crystal structure of [7b](CF3SO3)4, the
Ru–Ru separations being almost identical at 7.9 and 11.2 Å,
respectively.[23] In both structures, the triflate anions are
found between the rectangular channels. In [7b](CF3-
Scheme 2. Two-step synthesis of metalla-rectangle [Ru4(p-
iPrC6H4Me)4(µ-bpy)2(µ-C2O4)2]4+ (5b).[21] SO3)4, disordered water molecules are observed in the cat-
ionic molecular rectangles as compared to [10c](CF3SO3)4,
Using a similar approach as for the synthesis of rectangle for which no solvent molecules are observed in the cavity.
5b, Jin’s group has synthesised a series of metalla-rectangles However, these systems could be seen as cationic nanotubes
by the combination of the unsaturated dinuclear arene ru- and potentially used for storage of small anions or small
thenium clip 4⬘ and various linear bidentate pyridyl connec- neutral molecules.

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MICROREVIEW B. Therrien

Figure 5. Molecular structure of cation 10c with a view of the mo-

lecular channels along the b axis.[24]

As expected, the molecular structure of [8c](CF3SO3)4

shows a larger cavity (7.9 ⫻ 13.6 Å2), which can accommo-
date guest molecules[25] (see Figure 6). Upon crystallisation
of [8c](CF3SO3)4 in a chloroform/diethyl ether mixture, two
diethyl ether molecules are encompassed in the hydrophobic
cavity of cation 8c. A similar crystal packing has also been
observed in [8b](CF3SO3)4, in which highly disordered sol- Scheme 3. [2 + 2] photodimerisation of 11b to give 12b.[26]
vent molecules were found in the rectangular (13.5 ⫻ 7.9 Å2)
cavity,[23] thus confirming the potential of such systems for
iridium pentamethylcyclopentadienyl analogue [Ir4(C5Me5)4-
host–guest chemistry and storage possibilities.
(µ-tpcb)(µ-C2O4)2]4+, in which only the rctt-cyclobutane
isomer was observed.[27]

Arene Ruthenium Metalla-Prisms

The simplest three-dimensional construction that in-
volves the fewest components is the triangular prism. If the
components of the prism do not contain stereogenic ele-
ments and if the two planar triangular subunits are per-
fectly eclipsed, the triangular prism obtained is achiral.[28]
The same dinuclear arene ruthenium units 1, 2, 3 and 4
have been used to generate metalla-prisms. The synthesis of
these hexanuclear arene ruthenium trigonal-prismatic cages
can be divided into two routes (see Scheme 4): (A) the dinu-
Figure 6. Molecular structure of cation 8c showing two encapsu-
clear arene ruthenium units react with two tridentate li-
lated diethyl ether molecules.[25] gands prior to the addition of silver triflate or (B) the dinu-
clear arene ruthenium clips react with silver triflate before
Linear 4,4⬘-bipyridylethylene (bpe) connectors and oxal- addition of the tridentate panels. In most cases both syn-
ato bridging ligands allow the formation of the compact thetic routes work equally well, affording the desired as-
metalla-rectangle [Ru4(p-iPrC6H4Me)4(µ-bpe)2(µ-C2O4)2]4+ semblies in similar yield; however, only route A can be used
(11b), in which two olefin double bonds are perfectly posi- to afford chlorido-bridged triangular prisms.[29]
tioned parallel to each other.[26] These two olefin double The molecular structures of 14 and 15 are presented in
bonds can react in solution under UV irradiation to form Figure 7. The chlorido-bridged metalla-prisms [Ru6(p-
the intramolecular [2 + 2] cycloaddition adduct [Ru4(p- iPrC6H4Me)6(µ-4-tpt)2(µ-Cl)6]6+ (14b), [Ru6(C6Me6)6(µ-4-
iPrC6H4Me)4(µ-tpcb)(µ-C2O4)2]4+ [tpcb = tetrakis(4-pyr- tpt)2(µ-Cl)6]6+ (14c), [Ru6(p-iPrC6H4Me)6(µ-3-tpt)2(µ-Cl)6]
6+
idyl)cyclobutane] (12b), shown in Scheme 3. (15b) and [Ru6(C6Me6)6(µ-3-tpt)2(µ-Cl)6]6+ (15c) are ob-
The photodimerisation reaction in CD3OD of 11b to give tained in good yield from the dinuclear arene ruthenium
12b upon UV irradiation can be easily monitored by 1H complexes 1b or 1c and the corresponding 2,4,6-tri(pyridin-
NMR spectroscopy. The [2 + 2] cycloaddition reaction of 4-yl)-1,3,5-triazine (4-tpt) or 2,4,6-tri(pyridin-3-yl)-1,3,5-tri-
the olefin double bonds is followed by the disappearance of azine (3-tpt) ligands followed by the addition of AgCF3SO3
the signal of the olefin protons at δ = 7.49 ppm and with (Route A).[29]
the emergence of a new signal at δ = 4.99 ppm, which is The molecular structures of the two chlorido-bridged
assigned to the cyclobutane protons. Upon formation of metalla-prisms 14b and 14c are presented in Figure 8. Due
12b, diastereotopic protons are observed for the pyridyl to the proximity of the two 4-tpt units, strong parallel π-
groups, which suggests a non-equivalent environment. This stacking interactions between the aromatic rings are ob-
is in accordance with the X-ray structural analysis of the served. The centroid···centroid distances (3.4 Å) between

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Arene Ruthenium Cages: Boxes Full of Surprises

tion of the aromatic rings of the tritopic 4-tpt subunits is

observed, which created an additional three-bladed propel-
ler chirality element, a common feature in this kind of tri-
angular metalla-prism.[31] These two stereogenic elements
are observed in the solid state and seen to persist in solu-
tion, as evidenced by 1H NMR spectroscopic experiments
in the presence of the anionic chiral NMR solvating agent
∆-binphat.[30] The molecular structures of 16b and 16c have
been established by single-crystal X-ray structural analysis
of the triflate salts (see Figure 9). Surprisingly, despite a
metal–metal distance of about 5.5 Å, the two central tri-
azine units are very close. The centroid···centroid distance
between the two triazine moieties is only 3.4 Å in 16b and
3.8 Å in 16c, where the 4-tpt ligands adopt a slightly stag-
gered conformation. In 16b, the twist angle of the oxalato
clips is only 4.0°, whereas the pyridyl rings of the two 4-tpt
units are tilted by 16.6° out of the plane of the triazine ring,
while in 16c, the ruthenium oxalato clips are twisted by
20.5° out of the plane of the 4-tpt subunits and the pyridyl
rings are tilted by 36.1°. This deviation from a perfectly
Scheme 4. Two major synthetic routes to arene ruthenium metalla- eclipsed conformation of the trigonal metalla-prisms occurs
prisms. in order to improve the π-stacking interaction between the
two 4-tpt ligands.

Figure 7. Molecular structures of 14 and 15.[29]

the corresponding triazine rings are slightly shorter than

the average metal–metal distances of the chlorido bimetallic
connectors (3.7 Å). In these systems, a slight deviation from
a perfectly eclipsed conformation of the two 4-tpt subunits Figure 9. Molecular structures of 16b and 16c.[30]
is observed, giving rise to chiral systems.
The more spacious cationic hexanuclear metalla-prisms,
[Ru6(p-iPrC6H4Me)6(µ-4-tpt)2(µ-C6H2O4)3]6+ (17b), [Ru6-
(C6Me6)6(µ-4-tpt)2(µ-C6H2O4)3]6+ (17c), [Ru6(p-iPrC6H4Me)6-
(µ-4-tpt)2(µ-C6Cl2O4)3]6+ (18b) and [Ru6(C6Me6)6(µ-4-tpt)2-
(µ-C6Cl2O4)3]6+ (18c), incorporating p-cymene or hexa-
methylbenzene ruthenium building blocks bridged by 2,5-
dihydroxy-1,4-benzoquinonato or 2,5-dichloro-3,6-dihy-
droxy-1,4-benzoquinonato ligands and connected by two 4-
tpt subunits, have been synthesised by following the same
Figure 8. Molecular structures of 14b and 14c.[29] strategy (Route B).[32] The synthesis of derivative 17b is pre-
sented in Scheme 5. The encapsulation of a flat molecule
A more important deviation of the eclipsed conforma- within the cavity of these hexanuclear metalla-prisms can
tion is observed in the cationic triangular metalla-prisms either enhance or weaken the chirality.[31] Moreover, if the
[Ru6(p-iPrC6H4Me)6(µ-4-tpt)2(µ-C2O4)3]6+ (16b) and [Ru6- encapsulated molecule possesses the proper symmetry and
(C6Me6)6(µ-4-tpt)2(µ-C2O4)3]6+ (16c), which contain bridg- fits perfectly into the cavity, the triangular prismatic confor-
ing oxalato ligands.[30] In these systems, a concerted rota- mation can be locked, thus suppressing chirality.

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MICROREVIEW B. Therrien

Scheme 5. Synthesis of metalla-prism 17b.[32]

Figure 11. Molecular structure of [C18H6(OMe)6傺17b](CF3-
Indeed, these systems have allowed the permanent encap- SO3)6.[34]
sulation of large aromatic molecules such as pyrene
(C16H10), fluoranthene (C16H10), triphenylene (C18H12), single-crystal X-ray structural analysis (see Figure 12). The
benzo[e]pyrene (C20H12) and coronene (C24H12),[33] or the Pt(acac)2 complex is strongly held between the triazine units
encapsulation of functionalised triphenylene molecules hexa- of the 4-tpt ligands, the platinum triazine···centroid separa-
hydroxytriphenylene [C18H6(OH)6] and hexamethoxytriphen- tion being 3.4 Å. To accommodate the Pt(acac)2 complex
ylene [C18H6(OMe)6].[34] The structures of [C16H10傺17b]- within the cavity of 17b, the Ru2(µ-C6H2O4)2+ dinuclear
(CF3SO3)6 and [C20H12傺17b](CF3SO3)6, obtained by sin- units are tilted out of the plane of the 4-tpt subunits by as
gle-crystal X-ray structural analysis, are presented in Fig- much as 14°.
ure 10. However, despite the presence of these large aro-
matic molecules (pyrene and benzo[e]pyrene) in the cavity
of 17b, the staggered conformation of the two 4-tpt units
remains, thus conserving the chirality of the metalla-prism
17b.

Figure 12. Molecular structure of [(acac)2Pt傺17b]6+.[32]

The cytotoxic activities on human ovarian cancer cells of

the “complex-in-a-complex” derivatives [(acac)2M傺17b]6+
were evaluated in comparison with free M(acac)2. Like a
“Trojan Horse”, they allow non-water-soluble molecules
such as M(acac)2 to be taken up by cancer cells.[32] This
water-soluble metalla-prism is also used also to encapsulate
functionalised aromatic molecules (pyrene-R) in a manner
Figure 10. Molecular structures of [C16H10傺17b](CF3SO3)6 and
[C20H12傺17b](CF3SO3)6.[33]

Single-crystal X-ray structural analysis of the carceplex

system [C18H6(OMe)6傺17b](CF3SO3)6 has been performed
as well.[34] Because of its size and the presence of six meth-
oxy groups, the hexamethoxytriphenylene is strongly encap-
sulated in 17b, and the twists of the two 4-tpt units, as well
as the rotation of the pyridyl groups, are locked in this sys-
tem (see Figure 11). Therefore, this system shows no chiral-
ity in the solid state and crystallises in the trigonal space
group R3̄c.
The assembly of 17b can also be achieved in the presence
of the square-planar complexes Pd(acac)2 and Pt(acac)2
(acac = acetylacetonato) to give the “complex-in-a-com-
plex” cations [(acac)2Pd傺17b]6+ and [(acac)2Pt傺17b]6+.[32]
Both cations are isolated as their triflate salts. The molecu-
lar structure of [(acac)2Pt傺17b](CF3SO3)6 is confirmed by Figure 13. Molecular structure of [pyrene-R傺17b]6+.[33]

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 10990682c, 2009, 17, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.200900180 by Universitat Jaume I, Wiley Online Library on [16/09/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Arene Ruthenium Cages: Boxes Full of Surprises

such that the aromatic part is encapsulated (pyrenyl moiety) Using the same strategy but employing 2,5-dihydroxy-
while a functional group (R group) hangs out of the cage 1,4-benzoquinonato instead of oxalato bridges, we synthe-
(see Figure 13).[33] The encapsulation of methyl 4-(pyren-1- sised a series of cationic octanuclear metalla-boxes of the
yl)butanoate in 17b was confirmed by 1H NMR spec- general formula [Ru8(arene)8(µ-tpp-H2)2(µ-C6H2O4)4]8+
troscopy and ESI mass spectrometry. (20a: arene = C6H5Me; 20b: arene = p-iPrC6H4Me; 20c:
Work is currently in progress to encapsulate monofunc- arene = C6Me6, see Scheme 6).[41]
tionalised pyrene derivatives incorporating various bio-
logical groups to confirm the potential of these water-solu-
ble metalla-prisms to act as drug carriers.

Arene Ruthenium Metalla-Boxes

Self-assembly of transition-metal complexes with por-

phyrin and metalla-porphyrin ligands is receiving a great
deal of attention in chemical research. The self-assembly of
porphyrin-containing squares by metal-ion coordination
was first reported by Drain and Lehn in 1994.[35] The com-
bination of square-planar transition-metal coordination to
bind multifunctional porphyrin ligands in a linear fashion Scheme 6. Synthesis of metalla-boxes 20.[41]
(180°) or at right angles (90°) was cleverly exploited in that
Similarly, cationic metalla-boxes incorporating toluene
initial paper. Many groups have followed this square-planar
or p-cymene ruthenium building blocks bridged by 2,5-di-
transition-metal coordination strategy to build up porphy-
hydroxy-1,4-benzoquinonato ligands and connected by the
rin-containing molecular assemblies.[36] Studies involving
zinc metallo-porphyrin 5,10,15,20-tetra(4-pyridyl)por-
the introduction of octahedral transition metals to assemble phyrin-ZnII (tpp-Zn) tetradentate ligand were synthesised:
such systems appeared a few years later.[37] The fac-Re-
[Ru8(C6H5Me)8(µ-tpp-Zn)2(µ-C6H2O4)4]8+ (21a) and [Ru8-
(CO)3 corner system was exploited by Hupp,[38] while Ales- (p-iPrC6H4Me)8(µ-tpp-Zn)2(µ-C6H2O4)4]8+ (21b) (see Fig-
sio used the fac-RuCl2(Me2SO)3(CO) complex[39] to gener- ure 15).[42]
ate multiple porphyrin-containing molecular assemblies.
Similarly, arene ruthenium building blocks can be exploited
to generate metalla-boxes.
Last year, Jin and his co-workers synthesised the metalla-
box [Ru8(p-iPrC6H4Me)8(µ-tpp-H2)2(µ-C2O4)4]8+ (19b) [tpp-
H2 = 5,10,15,20-tetra(4-pyridyl)porphyrin] incorporating
tetradentate porphyrin ligands and oxalato bridging con-
nectors.[40] The molecular structure of 19b was determined
by X-ray structural analysis of its triflate salt (see Fig-
ure 14).

Figure 15. Molecular structures of 21a and 21b.[42]

The G-quadruplex motif has became a promising target

for cancer therapy, as G-quadruplexes inhibit the enzyme
telomerase, an enzyme involved in the immortality of can-
cer cells.[43] Until recently, G-quadruplex stabilisers were
purely organic molecules with large aromatic surfaces and
positive charges to interact with the grooves of the quadru-
plex.[44] These two features can be easily achieved by coordi-
nation chemistry. Indeed, square-planar metal complexes
Figure 14. Molecular structure of the metalla-box 19b.[40] with salphen- and salen-type ligands have been used suc-
cessfully to stabilise telomeric quadruplex DNA.[45] Simi-
The X-ray structural analysis of 19b showed the metalla- larly, the self-assembled square [Pt4(en)4(µ-bpy)4]4+, which
box to possess helical chirality, the porphyrin···porphyrin has been developed by Fujita,[1] showed a good binding af-
separation to be 4.1 Å and the volume of the box to be finity for G-quadruplexes.[46] Therefore, we were interested
approximately 800 Å3. Despite this large volume, the cavity in studying the ability of cationic octanuclear metalla-boxes,
of the octanuclear metalla-box was too narrow to accom- which possess large aromatic surfaces and are highly posi-
modate a guest molecule, and strong π-stacking interactions tively charged, to stabilise G-quadruplexes and to act as
between the two porphyrin panels were observed. telomerase inhibitors.[42]

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 10990682c, 2009, 17, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.200900180 by Universitat Jaume I, Wiley Online Library on [16/09/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
MICROREVIEW B. Therrien

The supramolecular metalla-boxes 20a, 20b, 21a and 21b 125, 9647–9652; e) J. D. Crowley, A. J. Goshe, B. Bosnich,
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