Self-assembly of bis-β-diketone-based [M2 L 2] dinuclear platforms into 2-dimensional coordination polymers

Article abstract of DOI:10.1039/c9ce00896a

A bis-β-diketone ligand incorporating a 3,5-substituted pyridine ring between its two β-diketone domains (1,1′-(pyridine-3,5-diyl)bis(4,4-dimethylpentane-1,3-dione), H₂L¹) and its interaction with three divalent cations (Cu²⁺, Zn²⁺ and Pd²⁺) is reported. Charge neutral dinuclear metallocycles of type [M₂L12] were obtained in each case and their X-ray structures determined. [Pd₂L12] incorporates two square-planar O₄-coordinated metal centres. The zinc(ii) and copper(ii) complexes contain five-coordinate O₄N₁-metal centres in which the pyridyl nitrogen from adjacent [M₂L12] metallocycles coordinates apically forming two-dimensional coordination polymers of type {[Zn₂L12]_n(dmf)_n} and {[Cu₂L12]_n(dmf)_n}. Desolvation of the coordination polymers led to loss of crystallinity.

Full text of DOI:10.1039/c9ce00896a

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PAPER
Yuan Zhuang et al.
Structural study on PVA assisted self-assembled 3D
hierarchical iron (hydr)oxides
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DOI: 10.1039/C9CE00896A
Journal Name
ARTICLE
Self-assembly of bis-ꢀ-diketone-based [M L ] dinuclear platforms
2
2
into 2-dimensional coordination polymers.
a,b
b
a*
A. J. Brock , John C. McMurtrie and J. K. Clegg
Received 00th January 20xx,
Accepted 00th January 20xx
A bis-ꢀ-diketone ligand incorporating a 3,5-substituted pyridine ring between its two ꢀ-diketone domains (1,1’-(pyridine-
1
2+
2+
2+
DOI: 10.1039/x0xx00000x
3,5-diyl)bis(4,4-dimethylpentane-1,3-dione), H
reported. Charge neutral dinuclear metallocycles of type [M
determined. [Pd ] incorporates two square-planar O -coordinated metal centres. The zinc(II) and copper(II) complexes
L1
contain five-coodinate O -metal centres in which the pyridyl nitrogen from adjacent [M ] metallocycles coordinate
L1
L1
(dmf) }. Desolvation of the
2
L ) and its interaction with a three divalent cations (Cu , Zn and Pd ) is
L1
] were obtained in each case and their X-ray structures
2
2
www.rsc.org/
2
2
4
4
N
1
2
2
apically forming two-dimensional coordination polymers of type {[Zn
coordination polymers led to loss of crystallinity .
2
L1
2
]
n
(dmf)
n
} and {[Cu
2
2
]
n
n
32, 34, 39, 41-
metallocycles together into extended architectures.
.
43
Introduction
The self-assembly of relatively simple molecules into larger
ordered structures through non-covalent interactions has
attracted interest over recent decades1 as these increasingly
complex systems have shown promise in a range of
, 2
3
,4
applications, from guest binding to separation to catalysis.
The resulting self-assembled systems, particularly those
incorporating metal-ions, have a wide range of architectural
5, 6
forms including discrete 2D and 3D cage-type structures as
well as coordination7, 8 and supramolecular polymers.
9,
10
Despite the considerable resources devoted to understanding
these systems, the predictable synthesis of multinuclear
architectures and control of the resulting properties still
remains a significant challenge.
β-Diketone ligands have been shown to produce a range of
metallo-supramolecular architectures in a largely predictable
manner, with a variety of potentially useful properties including
stimuli-responsive and guest-binding behaviour.1
1-30
The
predictable behaviour of these ligands originates from their
precise coordination vectors. For example, the reaction of H
with divalent metals produces charge-neutral [M
2
L
2 2
L ]
metallocyclic complexes.2
5,
31-40
In many cases, these
In an extension of these studies we report the preparation of
3,5-pyridine-spaced heterotopic pyridine/bis-β-diketone
metallocycles can be used as ‘platform’ components for the
hierarchical self-assembly of more elaborate systems; selected
hetero- or homotopic ancillary ligands can coordinate to the
axial coordination sites of the metal centres, linking these
a
1
ligand (H
2
L
) along with three of its divalent metal complexes
1
producing both a discrete [Pd
coordination polymers {[Zn
2
L
2
]
complex and two
1
1
2
L
2
]
n
(dmf)
n
} and {[Cu
2
L
2
]
n
(dmf)
n
}.
Experimental
a.School of Chemistry and Molecular Biosciences, The University of Queensland,
Materials and methods
St. Lucia, QLD, Australia 4072. j.clegg@uq.edu.au
School of Chemistry, Physics and Mechanical Engineering, Queensland
University of Technology, 2 George Street, Brisbane, QLD, Australia 4000
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
All reagents and solvents were obtained through commercial
sources unless otherwise stated. THF was dried using a PureSolv
solvent purification system (Innovative Technologies) prior to
use.
b
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Single crystals suitable for X-ray analysis were grown by slow
View Article Online
DOI: 10.1039/C9CE00896A
evaporation of an ethanol/water solution of the compound.
NMR spectra were collected on a Bruker AV300 spectrometer.
Chemical shifts are reported relative to the residual solvent
peak. ESI-MS was conducted on a Bruker HCT mass
spectrometer. Elemental analyses were undertaken by the
Microanalytical Service, School of Chemistry and Molecular
Biosciences, The University of Queensland.
Complex and coordination polymer synthesis
2 2 2
Synthesis of [Pd ]. H
L1 L1 (0.02 g, 0.06 mmol) was dissolved in
DMF (5 mL). Palladium(II) acetate (0.013 g, 0.06 mmol) was
dissolved in DMF (5 mL) and added to the ligand solution. This
mixture was sealed in a 20 mL vial and heated at 90 °C for 48 h,
over which time small yellow crystalline plates formed. After
cooling, the crystalline solid was collected by filtration and
washed with diethyl ether (0.022 g, 84 %). Anal. Calcd: C 52.36,
H 5.32, N 3.21 %. Found: C 52.51, H 5.58, N 3.34%. Due to the
limited solubility of this compound, NMR spectra could not be
successfully recorded. A single crystal was selected directly from
the reaction mixture for X-ray diffraction analysis.
Ligand Synthesis
Pyridine-3,5-dicarboxylic acid. Pyridine-3,5-dicarboxylic acid
was prepared via modified literature procedures.44 3,5-lutidine
(14.6 g, 0.136 mol) was dissolved in water (500 mL). Potassium
permanganate (86 g, 0.54 mol) was added and the reaction was
stirred at reflux for 16 h. After cooling, the reaction mixture was
filtered and the brown filtrate was extracted with NaOH (3 x 100
mL 1 M). After washing with chloroform (2 x 100 mL), the
combined aqueous phases were reduced to 200 mL and the pH
was adjusted to 5 with concentrated hydrochloric acid. The
aqueous phase was extracted with chloroform/isopropanol (4 x
L1
[Zn
2
2 n
] . (0.03 g, 0.09 mmol) was dissolved in DMF (3 mL) in a
0 mL glass vial. A solution of zinc(II) nitrate hexahydrate (0.051
2
g, 0.14 mmol) in DMF (2 mL) was added and the vial sealed. The
vial was then heated at 90 °C for 48 hours, over which time
yellow crystalline blocks were seen to appear. After cooling, one
of these crystals was selected for X-ray diffraction, while the
remainder were washed by soaking twice for 24 h in fresh DMF
and stored under DMF. Bulk product was collected by filtration
1
00 mL, 3:1 ratio) and the combined organic phases were
evaporated to dryness, yielding 15.28 g (67%) of white solid that
1
was used without further purification. H NMR agreed with
previously reported values.4 H NMR (DMSO-d
5 1
6
): 8.50 (t, 1 H),
8
.89 (d, 2 H).
and washed with DMF followed by diethyl ether. Yield: 0.024 g,
1
3
3%, Anal. Calcd for [Zn
2
L
2
]
n
∙DMF
n
: C 56.82, H 5.48, N 3.31 %
Diethyl pyridine-3,5-dicarboxylate. Pyridine-3,5-dicarboxylic
acid (5 g, 0.03 mol) was dissolved in ethanol (200 mL).
concentrated sulfuric acid (5.0 mL) was added and the solution
was stirred at reflux for 12 h. After cooling, the reaction mixture
was concentrated in vacuo to approximately 20 mL and
neutralised with aqueous sodium bicarbonate. The aqueous
phase was extracted with ethyl acetate (3 x 100 mL) and the
Found: C 56.69, H 5.83, N 3.52%.
Crystals of this complex could be obtained by a second method:
1
[
(
2
Pd L
2
] (5 mg, 5.7 μmol) and zinc(II) perchlorate hexahydrate
2.5 mg, 5.7 μmol) were suspended in DMF (20 mL) and sealed
in a glass vial, which was heated at 100 °C for 48 h. After this
time several pale yellow crystals were retrieved from
suspension in the colourless solution. Unit cell analysis of
several single crystals confirmed identity of the material.
combined organic phases were evaporated to dryness, yielding
1
5
.23 g (0.023 mol, 78%) of a crystalline white powder. H NMR
4
6 1
3
agreed with literature values. H NMR (CDCl ): 1.42 (t, 6 H),
4
.44 (q, 4 H), 8.85 (t, 1 H), 9.35 (d, 2 H).
L1
L1
[Cu
2
]
2 n
.
[Pd
2
2
] (5 mg, 5.7 μmol) and copper(II) perchlorate
hexahydrate (2.5 mg, 5.7 μmol) were dissolved in DMF (20 mL)
and sealed in a glass vial, which was heated at 100 C for 48 h.
After this time a very small quantity of dark green crystals were
retrieved from suspension in the dark brown/red bulk material.
Due to the small quantity isolated, only SCXRD was undertaken
on this material.
1
H
,1'-(Pyridine-3,5-diyl)bis(4,4-dimethylpentane-1,3-dione),
̊
1
2
L . Pinacolone (4.49 g, 0.045 mol) was dissolved in dry THF
(
30 mL), followed by the addition of sodium amide (5.0 g, 0.13
mol). The reaction was cooled to 0 °C and then diethyl pyridine-
,5-dicarboxylate (5.0 g, 0.022 mol) dissolved in dry THF (150
3
mL) was then added dropwise. After stirring for 12 h, allowing
to warm to room temperature over this time, the reaction was
quenched by the slow addition of ice water (50 mL) and acidified
to pH 6 with 1 M HCl(aq). The reaction mixture was extracted
with 3:1 chloroform/isopropanol (4 x 100 mL) and the combined
organic phases were evaporated to dryness. The orange, tacky
crude product was recrystallised from hot methanol, yielding
Crystallography
1
Data for H
2
L
was collected on an Oxford Diffraction Gemini II
Ultra diffractometer operating at graphite-monochromated Cu
Kα wavelength (T = 190(2) K). Data were indexed, reduced and
integrated using CrysAlisPro. SCXRD data for the transition
metal complexes were collected on the MX1 beamline at the
47
48
4
.31 g (0.013 mol, 59%) of a crystalline yellow solid. NMR
Australian Synchrotron (λ = 0.7108 Å, T = 100(2) K) and data
1
(MeOD-d
4
) H: 1.10 (s, 18 H), 6.48 (s, 2 H), 8.89 (t, 1 H), 9.23 (d,
49
were processed using XDS. All structures were solved using
1
3
2
2
4
H), C: 25.60, 40.12, 130.77, 132.22, 150.84, 151.48, 179.89,
50
SHELXT before refinement via full-matrix least-squares
-
05.44. ESI-MS: 330.3 [M-H] Anal. Calcd: C: 68.86, H: 7.60, N:
2
51
refinement against F using SHELXL-2014 using the Olex2
graphical user interface. . Where appropriate electron density
.23, O: 19.31 % ; Found: C: 68.69, H: 7.57, N: 4.33 %.
52
was identified in the Fourier difference map, oxygen-bound
hydrogen atoms were placed accordingly. Carbon-bound
2
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hydrogen atoms were placed in idealised positions and refined hydrogen atoms localised on the oxygen atoms closest to the
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using a riding model. Tabulated refinement statistics and a pyridyl group, in a similar fashion to relatDeOdI:li1g0a.1n0d3s9./
C9CE00896A
31
more detailed discussion of the refinement can be found in the
ESI. CIFs have been deposited with the Cambridge Structural
Database (CCDC 1914267-1914270).
O
O
Results and Discussion
O
O
KMnO
2
4
2 4
EtOH, cat. H SO
HO
OH
O
O
O
Previous studies have investigated the 2,6-disubstituted
H O
N
N
N
1
2 53
analogue of H
2 2
L (H L ) which has been used to form a number
III
2
3+
III
2 + 53-
of triple-stranded helicates of type [M
2
Ln
2
3 2 3
L ] or[M KL ]
O
O
1. NaNH
+
2
O
O
O
O
55
II
LnL2
3+ 56-60
and trinuclear ladder complexes [M
2
] ,
in which
2. H /H
2
O
2
O
O
the inwardly directed pyridyl electrons bind to the central metal
ion (Figure 1). We envisaged that changing the substitution of
the central pyridine unit to the 3,5-positions followed by
THF
N
N
1
2
Scheme 1. Synthetic route for H L .
reaction with a suitable metal might produce complexes of type
1
[
2
M L
2
] in which the projection of the Lewis basic pyridine N
Dimers of H
interlock in an archetypal herringbone motif. As is typical for
L1 interact via π-π interactions (3.55 Å) and
2
atoms were divergent. Such complexes then might prove
suitable either as metallo-ligands analogous to linear organic
bis(4-pyridyl) ligands such as 4,4’-bipyridine, or spontaneously
self-assemble into coordination polymers. While a range of
mono-β-diketones containing pyridyl functionality have been
2
5
these compounds.
19, 61-65
used to assemble coordination polymers,
dinucleating
bis-β-diketone ligands of this particular type have not yet been
studied for their self-assembly into coordination polymers,
although there is a report of a triple-stranded iron(III) helicate
2
4
containing a related ligand,
and one report of the
number of heterometallic
1
incorporation of
L
into
a
L1. Atoms are shown as thermal ellipsoids at 50%
2
Figure 2. X-ray crystal structure of H
macrocycles.66 The latter report provides no synthetic details probability. Only a single component of the rotationally disordered tert-butyl groups is
of the ligand or its homometallic complexes, nor any shown.
characterisation of them.
The reaction of H
was then investigated. We initially explored conditions
2 2
analogous to those employed for the preparation of [M L ]
L1 with palladium(II), copper(II) and zinc(II)
2
N
complexes with phenyl-spaced ligands (specifically slow
addition of metal ion to a THF solution of the ligand in the
presence of base), however, these yielded only intractable and
presumably polymeric solids. We then turned to solvothermal
methods.
N
N
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
M
M
M
M
The reaction of H
2
L1 with palladium(II) acetate (1 : 1) in DMF in
a sealed vial produced small single yellow-orange crystals of
crystallographic quality. The X-ray structure of this product
N
confirms the formation of a discrete dinuclear metallocyclic
Figure 1. Pyridyl nitrogen coordination vectors of divalent transition metal complexes of
L2 (left); and H L1 (right).
1
complex [Pd
2
L
2
] (Figure 3). Each palladium(II) centre is square
H
2
2
planar and the two divergent pyridyl nitrogens are directed at
approximately 180 from each other. The nitrogen-nitrogen
̊
H
2
L1 was prepared in three steps from 3,5-lutidine (Scheme 1).
distance is 10.85 Å, 3.98 Å longer than the classical linear
The expected enol singlet was not observed at ca. 16 ppm in the
bridging ligand 4,4’-bipyridine. We then explored the potential
1
H NMR spectrum due to H-D exchange with the deuterated
1
to use [Pd
2
L
2
] as a metallo-ligand through the addition of
methanol solvent, however the structure was unambiguously
confirmed by X-ray crystallography. Slow evaporation of an
ethanol/water solution of the compound yielded large, pale
yellow single crystals which were of suitable quality for
various transition metals. The studies were not successful as
1
[
2
Pd L
2
] was found to have extremely limited solubility in
common laboratory solvents, even at elevated temperatures.
diffraction studies.
1
2
H L
crystallises in P2
1
/n with a complete ligand in the
asymmetric unit (Figure 2). The crystal structure shows that the
molecule crystallises as the bis-enol tautomer, with the enol
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DOI: 10.1039/C9CE00896A
2 2
Figure 3. Single crystal X-ray structure of [Pd ]. The asymmetric unit comprises one
L1
palladium(II) ion and one ligand. H atoms have been omitted for clarity.
1
n n
Figure 5. Expanded top-down view of 2D sheet of {[Zn2L 2] (dmf) }. H atoms have been
omitted for clarity.
Heating equimolar quantities of H
led to the formation of a yellow crystalline solid. The X-ray The network is composed of a series of infinite, stepped, one-
L1 and zinc(II) nitrate in DMF
2
1
1
2 2 2 2
crystal structure of this material (Figure 4) showed that it was a dimensional chains of [Zn L ] groups bridged by further [Zn L ]
1
units, which are then cross-linked into a two-dimensional
coordination polymer of formula {[Zn
2 2 n n
L ] (dmf) }. The product
has five-coordinate zinc(II) centres with the four
ꢀ
-diketone network by identical chains running perpendicular to the
oxygen atoms in the basal-plane and with the apical position direction of propagation (Figure 5). The topology of this
network is non-trivial, and a simplified diagram is shown in
metallocycle. The nitrogen ligands are arranged mutually anti Figure S1 (ESI). Simplification of each metallocycle to a 4-
connecting node results in a simple sql topology, however a
1
2 2
occupied by a pyridyl nitrogen atom from an adjacent [Zn L ]
1
2 2
across the plane of the [Zn L ] unit. A two-dimensional
coordination polymer results, as opposed to the one- more accurate description may be gained by treating each
dimensional polymers typically observed upon coordination of zinc(II) centre as a five-connecting node, in which case the
3
2, 34
topology is that of the relatively uncommon tts net.67 The
2 2
a ditopic ancillary ligand to an [M L ] platform of this type.
windows defined by this cross-linking are rhomboidal in shape,
and are bounded on four edges by pyridyl rings. These spaces
3
represent approximately 20 % (450 Å ) of the unit cell volume
and are occupied by disordered DMF molecules that are
situated on a crystallographic inversion centre. Crystals of this
compound were stable under ambient conditions for several
minutes, eventually losing single crystallinity, presumably due
to desolvation and collapse of the network.
We then examined similar reaction conditions used to prepare
1
2
{[Zn L
2
]
n
(dmf)
n
} with other divalent first-row transition metal
complexes including copper(II), nickel(II) and cobalt(II),
Figure 4.Top-down (left) and side-on (right) views of the [Zn
2
L1
2
] metallocyclic unit of however, no crystalline materials were obtained.
The
L1
1
the {[Zn
2
2 n n
] (dmf) } coordination polymer. Only one component of disordered tert-butyl
solvothermal reaction of [Pd
2
L
2
] with copper(II) perchlorate in
groups is shown. H atoms have been omitted for clarity.
DMF led to the isolation of a small quantity of green crystals.
The X-ray structure of these crystals, showed that the material,
1
{
[Cu
2
L
2
]
n
(dmf)
n
}, is isomorphous with the previously discussed
zinc(II) complex (Figure 6). Repetition of this experimental
protocol with the corresponding zinc(II) salt rather than copper
returned several pale yellow crystals which were confirmed as
1
2
{[Zn L
2
]
n
(dmf)
n
} by unit cell analysis. This method uniformly
produced only very small quantities of crystalline product.
4
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G. Y. Wu, L. J. Chen, L. Xu, X. L. Zhao and H. BV.ieYwaAnrgtic,leCoOonlrinde.
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Figure 6. Two-dimensional network of {[Cu ] (dmf) }, top-down view. Only a single
L1
component of rotational disorder is shown and H atoms are omitted for clarity.
1
4.
R. T. W. Scott, L. F. Jones, I. S. Tidmarsh, B. Breeze, R. H.
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Conclusions
1
1
5.
6.
The synthesis of a 3,5-subsituted pyridine -bis-β-diketone ligand
has been reported along with three of its transition metal
1
1
1
complexes [Pd
2
L
2
], {[Zn
2
L
2
]
n
(dmf)
n
} and {[Cu
2
L1
L
2
2
]
n
(dmf)
n
}. In
17.
the polymeric systems the metallocyclic [M
2
] unit acts as
both a ‘platform’ and a metalloligand. Studies investigating the
1
997, 1561-1562.
1
interaction of H
2
L
with trivalent metal ions are underway along
1
8.
A. P. Bassett, S. W. Magennis, P. B. Glover, D. J. Lewis, N.
Spencer, S. Parsons, R. M. Williams, L. De Cola and Z.
Pikramenou, J. Am. Chem. Soc., 2004, 126, 9413-9424.
L. Carlucci, G. Ciani, D. M. Proserpio and M. Visconti,
CrystEngComm, 2011, 13, 5891-5902.
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Renouf, C. Richardson and A. J. Stevenson, Chem.
Commun., 2010, 46, 5067-5069.
1
with further derivatisation to increase the solubility of [M
2
L
2
].
The resulting complexes might prove suitable as metallo-ligands
for the predictable formation of increasing complex functional
materials.
1
2
9.
0.
Acknowledgements
2
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CrystEngComm
View Article Online
DOI: 10.1039/C9CE00896A
bis-훃-diketone [M L ] dinuclear platforms self-assemble into 2-dimensional coordination
2
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