A three-dimensional cubic halogen-bonded network

Article abstract of DOI:10.1039/c8cc02178c

The rational, deliberate design of supramolecular architectures is of great importance for the discovery of complex materials. A three-dimensional cubic halogen-bonded network has been prepared by combination of an octahedral metal-containing halogen bond acceptor and a linear ditopic donor. This material displays α-Po pcu topology and is seven-fold interpenetrated. This is the first neutral, metal-containing three-dimensional halogen-bonded network to be reported.

Full text of DOI:10.1039/c8cc02178c

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A three-dimensional cubic halogen-bonded network
Joshua J. Brown,a Aidan J. Brock,a Michael C. Pfrunder,a Arnaud Grosjean,a John Ward,a John C.
McMurtrie,*,b and Jack K. Clegg,*,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The rational, deliberate design of supramolecular network architectures comprised of these components is yet
architectures is of great importance for the discovery of to be achieved.24-27 Here we present the first example of a
complex materials.
A three-dimensional cubic halogen- charge neutral, three-dimensional cubic halogen-bonded
bonded network has been prepared by combination of an network.
octahedral metal-containing halogen bond acceptor and a
We reasoned that co-crystallisation of a combination of
linear ditopic donor. This material displays α-Po pcu topology octahedral and linear topological components in the
and is seven-fold interpenetrated. This is the first neutral, appropriate ratio required to form saturated halogen bonds
metal-containing
three-dimensional
halogen-bonded (i.e. donor : acceptor) would produce a halogen-bonded
network to be reported.
network with an
1). 4,5
α
-Po (primitive cubic, pcu) topology (Figure
25, 28
The controlled arrangement of molecules in a predictable
We selected [Fe(bppd)3],24,
1, to act as the six-fold
fashion is a fundamental step in the development of stimuli- halogen bond acceptor as it contains six divergent pyridyl
responsive functional materials and underpins many biological nitrogens arranged approximately octahedrally and chose 1,4-
functions.1-4 Network materials in particular often respond to diiodotetrafluorobenzene (1,4-DITFB,
2
) as a linear halogen
the application of light, magnetic fields and temperature or bond donor. The combination of 4-pyridyl-substituted organic
pressure in unusual ways leading to properties such as ligands (including bppdH) and has been previously shown to
flexibility, extreme positive or negative thermal expansion and reliably form linear halogen bonds (i.e. the average of the C4-
compressibility.5-8 Complex materials of this type have a wide N···I and N···I-C angles approximate 180 °) 29, 30
2
.
range of applications including sensing, selective guest
uptake/release and aero-space engineering.5, 9-11
Figure 1. The combination of an octahedral and a linear component should lead to the
The complexity of such networks provides synthetic
challenges particularly where a desired architecture and
specific properties are required. One of the most successful
approaches to the controlled synthesis of these systems is the
net-based approach which was proposed by Robson12, 13 and
later developed into a reticular approach.14 These approaches
have yielded
a plethora of metal-containing networks.
Rationally controlling the formation of three-dimensional
assemblies relying on intermolecular interactions such as
hydrogen bonds or halogen bonds, which are weaker and
more labile than coordinate bonds, are far less explored.15-20
While a number of metal-containing halogen-bonded systems
have been reported,21-23 the predictable design of complex
formation of a cubic supramolecular network.
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Journal Name
undergo a combination of
π-π and CH-π interactions with
adjacent networks. We infer that the high degree of
interpenetration arises from the large aspect ratio of the 1,4-
DITFB linkers relative to that of the [Fe(bppd)3] units producing
an “open” network.
By combining
1 and 2 in 1:3 molar ratio (that is, a 1:1 N to I
ratio) in a 10:1 acetone/water solution and allowing slow
evaporation of the acetone, red block-like crystals suitable for
X-ray analysis were retrieved with quantitative yield. The
resulting
crystallises in the space group P21/c (Figure S1 in the ESI†). As
expected, each of the six pyridyl nitrogen atoms of forms a
single halogen bond with iodine atoms from six different
molecules of (average N∙∙∙I distance 2.81(4) Å) such that all
nitrogen and iodine atoms are involved in halogen bonding
interactions. The result is that each molecule of acts as a
linear di(halogen bond) bridge between adjacent octahedral
[Fe(bppd)3] complexes. An infinite cubic network with a -Po
pcu topology (point symbol 412.63) results (Figure 2). The
iron(III) centres are separated by 25.25 – 25.96 Å and are
located on the corners of the cubic array with the 1,4-DITFB
molecules arranged along the edges. The network is not
perfectly cubic, but instead has a rhombohedral distortion
material
[Fe(bppd)3](1,4-DITFB)3
∙
0.5H2O,
3,
1
2
Figure 3. Schematic representation of the seven-interpenetrated networks in
One rhombohedral sub-unit of each network is shown in a different colour.
3.
2
We have reported the first rational, deliberate design of a
cubic coordination compound-based halogen bonded network,
which was achieved by a symmetry interaction or reticular
synthesis approach similar to that used for coordination
polymer design. This material represents the first example of a
new class of three-dimensional, charge neutral metal-
containing architectures formed using supramolecular
interactions. One advantage of these systems over those
relying on coordination-bonds for network assembly may stem
from the improved inherent error checking capabilities of the
labile halogen bond and the resulting potential for isolation of
these complex products in quantitative yields under mild
reaction conditions.
α
We thank the Australian Research Council, the Central
Analytical Research Facility, Queensland University of
Technology and the University of Queensland for support.
Conflicts of interest
There are no conflicts to declare.
with Fe-Fe-Fe angles of between 43 and 113 °.
Figure 2. Repeating rhombohedral subunit in the three-dimensional halogen bonded
pcu network of 3 (water molecules not shown).
Notes and references
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fold (class Ia) interpenetrated structure31 (Figure 3 and Figure
S2 in the ESI†). Each of the interpenetrated frameworks
,
2 | J. Name., 2012, 00, 1-3
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