Synthetic Considerations in the Self-Assembly of Coordination Polymers of Pyridine-Functionalized Hybrid Mn-Anderson Polyoxometalates

Article abstract of DOI:10.1021/acs.cgd.7b00672

The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs such as metal-organic frameworks (MOFs) is desirable for a range of applications where intrinsic properties inherited from both the MOF and POM are utilized, including catalysis and magnetic data storage. The controlled self-assembly of targeted MOF topologies containing POM units is hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as coordinating groups toward linking metal cations leading to a diverse range of structures, but incorporation of organic donor units into hybrid POMs offers an alternative methodology to programmably synthesize POM/MOF conjugates. Herein, we report six coordination polymers obtained serendipitously wherein Zn²⁺ and Cu²⁺ link pyridine-appended Mn-Anderson clusters into two- and three-dimensional network solids with complex connectivities and topologies. Careful inspection of their solid-state structures has allowed us to identify common structure-directing features across these coordination polymers, including a square motif where two Zn²⁺ cations bridge two POMs. By correlating certain structural motifs with synthetic conditions, we have formulated a series of design considerations for the self-assembly of coordination polymers of hybrid POMs, encompassing the selection of reaction conditions, coligands, and linking metal cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid POMs into functional MOF materials.

Full text of DOI:10.1021/acs.cgd.7b00672

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Article
Synthetic Considerations in the Self-Assembly of Coordination Polymers
of Pyridine-Functionalised Hybrid Mn-Anderson Polyoxometalates
Francois-Joseph Yazigi, Claire Wilson, De-Liang Long, and Ross S. Forgan
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b00672 • Publication Date (Web): 19 Jul 2017
Downloaded from http://pubs.acs.org on July 23, 2017
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Synthetic Considerations in the SelfꢀAssembly of
Coordination Polymers of PyridineꢀFunctionalised
Hybrid MnꢀAnderson Polyoxometalates
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FrançoisꢀJoseph Yazigi, Claire Wilson, DeꢀLiang Long, Ross S. Forgan*
WestCHEM School of Chemistry, University of Glasgow, Joseph Black Building, University
Avenue, Glasgow, G12 8QQ, UK
KEYWORDS: Polyoxometalates; metalꢀorganic frameworks; selfꢀassembly; coordination
networks; solidꢀstate structures.
The incorporation of polyoxometalates (POMs) as structural units into ordered porous constructs
such as metalꢀorganic frameworks (MOFs) is desirable for a range of applications where intrinsic
properties inherited from both the MOF and POM are utilised, including catalysis and magnetic
data storage. The controlled selfꢀassembly of targeted MOF topologies containing POM units is
hampered by the wide range of oxo and hydroxo units on the peripheries of POMs that can act as
coordinating groups towards linking metal cations leading to a diverse range of structures, but
incorporation of organic donor units into hybrid POMs offers an alternative methodology to
programmably synthesise POM/MOF conjugates. Herein, we report six coordination polymers
2+
2+
obtained serendipitously wherein Zn and Cu link pyridineꢀappended MnꢀAnderson clusters
into twoꢀ and threeꢀdimensional network solids with complex connectivities and topologies.
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Careful inspection of their solidꢀstate structures has allowed us to identify common structureꢀ
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directing features across these coordination polymers, including a square motif where two Zn
cations bridge two POMs. By correlating certain structural motifs with synthetic conditions we
have formulated a series of design considerations for the selfꢀassembly of coordination polymers
of hybrid POMs, encompassing the selection of reaction conditions, coꢀligands and linking metal
cations. We anticipate that these synthetic guidelines will inform the future assembly of hybrid
POMs into functional MOF materials.
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INTRODUCTION
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ꢀ3
Polyoxometalates (POMs) are soluble molecular oxides of dꢀblock transition metals in high
VI
V,VI
IV,V
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oxidation states (e.g. W , Mo , V ) that have been widely studied for their catalytic,
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magnetic,
photochromic
and redox properties.
Given their large range of their
chemical and physical properties, their incorporation into MetalꢀOrganic Frameworks (MOFs) –
network structures composed of metal clusters or metal ions connected by organic linkers – or
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more generally into porous frameworks has been investigated.
Creating POM/MOF
conjugate materials can associate their individual properties, for instance the catalytic properties
31
of a POM with the large surface area of a MOF, or achieving a synergistic effect, for example
3
2
the cooperative effect of single molecule magnets or enhanced photocatalytic proton
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reduction. To do so, two main approaches have been followed to date (Figure 1a). The first is
the impregnation of the POMs into the pores of a MOF, where POMs are either added during the
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MOF synthesis and trapped in the pores,
or they are inserted postsynthetically by soaking the
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MOF in a solution of the desired POM.
The second approach is to consider POMs as
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building blocks for porous structures, with the aim of creating a bond between the POM and
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either an organic linker (usually a multitopic carboxylic acid or Nꢀdonor ligand)
or a
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transition metal.
The terminal oxygen atoms or hydroxyl groups of POMs can be substituted
by the oxygen atoms of carboxylates, while capping transition metals in some POM species can
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be chelated by organic ligands, leading to extended frameworks.
Although this approach can
allow rational design of desired structures by assessing the geometries and the coordination
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numbers of the secondary building units (POM and linker)
materials may form serendipitously.
it is often not the case, and
Figure 1. a) Schematic illustration of three possible routes to incorporate POMs into MOFs.
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Representations of the solidꢀstate structures and lengths of b) the amidoꢀlinked POM-1 and c)
the shorter, linear POM-2, in comparison to d) N,N’ꢀdiꢀ(4ꢀpyridyl)ꢀ1,4,5,8ꢀ
naphthalenetetracarboxydiimide (DPNI), widely used as a pillar molecule in the synthesis of
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An alternative, third approach is to use hybrid POMs that already have organic ligands
grafted onto the inorganic cluster and that can be conceived and synthesised in a predefined
geometry, with extended metal chelating units arranged in a similar manner to conventional,
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purely organic linkers. Hasenknopf et al. have used this strategy to show that bisꢀpyridyl
modified Lindqvistꢀtype hybrid POMs can selfꢀassemble into triangles through coordination to
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Pd cations, as have Izett et al. with bisꢀpyridyl functionalised Dawson clusters. Peng et al.
reported solution phase coordination polymers of bisꢀterpyridyl appended hexamolybdates
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connected by Fe units, while Hill et al. reported the linking of bisꢀpyridylꢀcapped
hexavanadate POMs by transition metals into one dimensional crystalline coordination
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polymers. Andersonꢀtype heteropolyoxomolybdates can easily be functionalised by trisꢀalkoxo
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ligands to incorporate chelating units
and, as such, we have selected two different pyridine
functionalised hybrid MnꢀAnderson POMs, with wellꢀdefined coordination sites, as potential Nꢀ
donor linkers for selfꢀassembly of MOFs (Figures 1b and 1c). The amidoꢀpyridyl trisꢀalkoxo Mnꢀ
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Anderson (POM-1) has been reported previously and shown to assemble into a gel upon
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addition of Pd , but the amide group introduces a kink in the linear geometry, so POM-2 was
prepared as an alternative, linear linker, which is closely related in size and geometry to the wellꢀ
established N,N’ꢀdiꢀ(4ꢀpyridyl)ꢀ1,4,5,8ꢀnaphthalenetetracarboxydiimide (DPNI) molecule
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(
Figure 1d). Both POMs were isolated as tris tetraꢀnꢀbutylammonium (TBA) salts, for superior
solubility in organic solvents. In the course of this study, POM-2 was independently reported
and shown to selfꢀassemble into coordination polymers linked by Cu I secondary building units
x x
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x = 2, 4). Our own preparation resulted in the isolation of a new crystalline solvate,
(
TBA) POM-2·Et O (see Supporting Information, Section S1).
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We report herein the materials serendipitously obtained while attempting to prepare threeꢀ
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dimensional “pillared” MOFs
comprised of dicarboxylic acid ligands such as biphenylꢀ
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,4ʹꢀdicarboxylic acid and the hybrid bisꢀpyridyl POM pillars linked by Zn and Cu paddlewheel
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clusters. A thorough examination of their solidꢀstate structures is presented, which has allowed
us to isolate recurring structural features and elucidate synthetic considerations for incorporation
of hybrid POMs into coordination polymers.
EXPERIMENTAL
All chemicals were purchased from SigmaꢀAldrich and were used without further purification.
Column chromatography was performed with Merck 60 silica gel (230–400 mesh). TBA [αꢀ
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Mo O ] and (TBA) POM-1 were synthesised according to literature procedures. NMR
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spectra ( H and C) were recorded on a Bruker AVI 500 MHz spectrometer and referenced to
residual solvent peaks. Thermogravimetric Analysis (TGA) measurements were carried out using
a TA Instruments Q500 Thermogravimetric Analyser. Measurements were collected from room
temperature to 1000 °C with a heating rate of 10 °C / min under an N atmosphere. Single crystal
2
Xꢀray diffraction (SCXRD) data for 1 were collected using a Rigaku AFC12 goniometer
equipped with an enhanced sensitivity (HG) Saturn724+ detector mounted at the window of an
FRꢀE+ SuperBright molybdenum rotating anode generator with VHF Varimax optics (70 µm
focus) equipped with an Oxford Cryosystems cryostream device. Data for 2 were collected using
a Bruker ApexII CCD diffractometer with Imus Mo microfocus source, and data for 3, 4 and 6
were collected using a Nonius KappaCCD diffractometer with a Mo sealed tube source and both
equipped with an Oxford Cryosystems Cryostream. Data for 5 were collected using a Bruker
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D8Venture with a dual Imus 3.0 microfocus source and Photon II CMOS detector equipped with
an Oxford Cryosystems nꢀHelix. Data for (TBA) POM-2·Et O were collected using an Agilent
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Xcalibur Gemini ultra diffractometer equipped with an Atlas CCD and Oxford Cryosystems
Cryostream. Details for all structures are given in the CIFs and a summary provided in the
Supporting Information (Tables S1 and S2) with further details for individual structures given
below. Elemental analysis was performed by MEDAC Ltd (http://medacltd.com/). Fourier
transform infrared spectroscopy (FTꢀIR) measurements were carried out on a Thermo Scientific
Nicolet iS5 FTꢀIR Spectrometer. High resolution electrospray ionisation mass spectroscopy
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(ESIꢀHRMS) was carried out using a Bruker Daltonics ꢀ micrOTOFꢀspectrometer in negative ion
polarity mode. N adsorption isotherms were carried out at 77 K on a Quantachrome Autosorb iQ
2
gas sorption analyser. Samples were degassed under vacuum at 120 °C for 20 h using the internal
turbo pump.
4-(tris-Hydroxymethyl)methylpyridine. 4ꢀMethylpyridine (4.18 mL, 45 mmol) was refluxed
in a 37% formaldehyde solution (54 mL, 720 mmol) for 24 h. The solution was cooled to room
temperature, and evaporated in vacuo to give a white paste. The white paste was dispersed in
MeOH (20 mL) which was subsequently evaporated in vacuo. This step was repeated three
times. The crude product was purified by silica gel column chromatography (80:20
1
DCM:MeOH) to give the desired product (5.08 g, 62%). H NMR (d ꢀDMSO) δ/ppm: 8.43 (dd,
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2H, J = 6.3, 1.6 Hz), 7.40 (dd, 2H, J = 6.3, 1.7 Hz), 4.52 (t, 3H, J = 4.52 Hz), 3.7 (d, 6H¸ J = 5.2
1
3
Hz). C NMR (d ꢀDMSO) δ/ppm: 152.4, 148.6, 123.4, 62.5, 49.5. The spectral data matched that
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from the literature.
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(
TBA) POM-2 ([N(C H ) ] [MnMo O {(OCH ) -C-C H N} ]). TBA [αꢀMo O ] (4.9 g,
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9 4 3
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2 3
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2
.34 mmol), [Mn(CH COO) ]·2H O (0.915 g, 3.41 mmol) and 4ꢀ(trisꢀ
3 3 2
hydroxymethyl)methylpyridine (1.5 g, 8.18 mmol) were added into a twoꢀneck roundꢀbottom
flask and refluxed in 165 mL of acetonitrile under nitrogen atmosphere overnight. The solution
was cooled to room temperature and the orange solid was filtered off. The orange solid was
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2ꢀ
mixed with an offꢀwhite powder, likely [Mo O ] , that was removed by successive addition of
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acetonitrile, to create a suspension of the white solid that was then pipetted out. When no more
pale powder was detected, the orange solid was filtered and redissolved in 80 mL of
dimethylformamide. The pure product crystallises as orange blocks by vapour diffusion of
1
diethyl ether (2.60 g, 75.4% based on Mo). H NMR in d ꢀDMSO δ/ppm: 63.7 (s, 12H), 7.9 (s,
6
ꢀ
4
H), 6.8 (s, 4H), 2.9 (s, 24H), 1.34 (s, 24H), 1.07 (s, 24H), 0.7 (s, 36H). Selected IR peaks (cm
1
)
: 2957 (m, s), 2872 (m, s), 2245 (w, s), 1593 (m, s), 1545 (w, s), 1477 (m, s), 1411 (w, s), 1378
(w, s), 1157 (w, s), 1066 (s, s), 939 (s, s), 918 (s, s), 901 (s, s), 816 (m, s), 787 (w, s), 737 (w, s),
ꢀ
6
54 (s, s), 561 (m, s). ESIꢀMS (ꢀ): m/z (calculated / found) [(TBA) POM-2] (1763.986 /
2
ꢀ
2ꢀ
1
763.9726); [H(TBA)POM-2] (1521.707 / 1521.7073), [(TBA)POM-2] (761.350 / 761.3592).
Elemental analysis % calcd for (TBA) POM-2 (C H MnMo N O ·C H NO): C, 39.85; H,
3
66 128
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24
3
7
6
.54; N, 4.04; Mn, 2.64; Mo, 27.69. Found: C, 39.90; H, 6.54; N, 4.26; Mn, 2.59; Mo, 25.61.
Crystal data for (TBA) POM-2. C H MnMo N O ·C H O, M = 2080.43, Triclinic, Pꢀ1, a =
3
66 128
6
5
24
4
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r
1
2.9854 (2) Å, b = 18.4763 (3) Å, c = 19.4549 (3)Å, α = 83.4319 (14) °, β = 75.1656 (14) °, γ =
3
7
5.0166 (14) °, V = 4352.87 (12)Å , T = 150 K, Z = 1, 71916 measured reflections, 17050 unique
(R = 0.036), which were used in all calculations. The final R = 0.028 for 14743 observed data
int
1
2
2
2
R[F > 2σ(F )] and wR(F ) = 0.067 (all data).
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Compound 1. (TBA) POM-1 (105.5 mg, 0.05 mmol), biphenylꢀ4,4′ꢀdicarboxylic acid (24 mg,
3
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.1 mmol) and 10 mL of DMF were added into a 50 mL topꢀscrew jar and the suspension was
sonicated for five minutes until all the reactants are dissolved. Then Zn(NO ) ·6H O (30 mg, 0.1
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mmol) was added and the solution was stirred for two minutes. A precipitate was formed and the
jar was sealed, placed in a preꢀheated oven at 80 °C and allowed to heat overnight. Compound 1
(
[(Me NH )Zn(POM-1)(DMF) ] ) separated as orange blocks, alongside colourless material
2 2 4 n
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ꢀ1
which was identified by elemental analysis to be IRMOFꢀ9. Selected IR peaks (cm ): 2929 (w,
b), 1650 (s s) 1602 (m, s), 1545 (w, s), 1495 (w, s), 1382 (s, s), 1287 (w, s), 1253 (m, s), 1178
(
w, s), 1092 (s, s), 1062 (w, s), 1026 (w, s), 1006 (w, s), 938 (m, s), 899 (w, s), 858 (w, s), 840
w, s), 797 (w, s), 771 (s, s), 681 (w, s), 657 (s, s), 564 (w, s). Elemental analysis % calcd for
(
(1) (IRMOFꢀ9) (C H MnMo N O Zn) (C H O Zn ) ·(C H NO) ): Mn, 1.80; Mo,
0
.5
0.5
34 58
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0.5 42 24 13
4 0.5
3
7
2
1
8.82; Zn, 10.69. Found: Mn, 1.93; Mo, 18.47; Zn, 11.04. Crystal Data for 1.
C H MnMo N O Zn·(C H NO) , M = 2134.32, Triclinic, Pꢀ1, a = 9.5486 (3) Å, b = 13.4333
34 58
6
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3
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r
(
3) Å, c = 16.3922 (5) Å, α = 69.045 (2) °, β = 74.330 (2) °, γ = 84.866 (2) °, V = 1890.51 (10)
3
Å , T = 100 K, Z = 1, 39074 measured reflections, 8594 unique (R = 0.028), which were used
int
2
2
2
in all calculations. The final R = 0.029 for 7834 observed data R[F > 2σ(F )] and wR(F ) =
1
0
.073 (all data).
Compound 2. (TBA) POM-1 (105.5 mg, 0.05 mmol) and biphenylꢀ4,4′ꢀdicarboxylic acid (24
3
mg, 0.1 mmol) were dissolved in 15 mL of DMF and the solution was added to a test tube. 5 mL
of DMF were carefully layered above the orange solution. A final solution of Zn(NO ) ·6H O
3
2
2
(30 mg, 0.1 mmol) in 15 mL of DMF was layered above the other solutions, and the test tube
was left to stand at room temperature. Compound 2 ([Zn (POM-1) (DMF) ] ) separated as
3
2
10 n
ꢀ1
orange blocks. Selected IR peaks (cm ): 3472 (w, b), 2930 (w, s), 1645 (s, s), 1542 (w, s), 1495
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3
4
5
6
7
8
9
(
w, s), 1436 (w, s), 1411 (w, s), 1384 (m, s), 1325 (w, s), 1287 (w, s), 1253 (m, s), 1094 (m, s),
1
063 (w, s), 1028 (m, s), 938 (m, s), 938 (m, s), 912 (s, s), 898 (s, s), 811 (w, s), 764 (w, s), 656
(s, s), 565, (w, s). Elemental analysis % calcd for 2 (C H Mn Mo N O ): Mn, 3.01; Mo,
7
0
114
2
12 18 62
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
3
1.48; Zn, 5.36. Found: Mn, 3.22; Mo, 31.25; Zn, 4.66. Crystal data for 2.
C H Mn Mo N O Zn M = 3657.06, Triclinic, Pꢀ1, a = 13.2866 (9) Å, b = 14.9514 (13) Å,
70
114
2
12 18 62
3,
r
3
c = 22.8017 (18) Å, α = 100.274 (5) °, β = 94.313 (5) °, γ = 94.534 (5) °, V = 4424.6 (6) Å , T =
150 K, Z = 1, 54322 measured reflections, 16564 unique (R = 0.117), which were used in all
int
2
2
2
calculations. The final R = 0.084 for 7186 observed data R[F > 2σ(F )] and wR(F ) = 0.274 (all
1
data).
Compound 3. Zn metalated 5,10,15,20ꢀtetra(4ꢀpyridyl)ꢀ21H,23Hꢀporphine (18 mg, 26 ꢀmol)
and 10 mL of DMF were added into a 50 mL topꢀscrew jar and the suspension sonicated for 10
min. (TBA) POM-2 (106 mg, 0.05 mmol) was added to the suspension and the jar sonicated
3
again for 5 min. Finally Zn(NO ) ·6H O (31 mg, 0.11 mmol) was added to the suspension and
3
2
2
the jar sonicated for a final 5 min. The jar was sealed, placed in a preꢀheated oven at 80 °C and
allowed to heat overnight. Compound 3 ([Zn (POM-2) (DMF) ] ) crystallised as orange blocks.
3
2
10 n
ꢀ1
Selected IR peaks (cm ): 2930 (w, b), 1639 (s, s), 1548 (w, s), 1497 (m, s), 1435 (m, s), 1418
m, s), 1378 (s, s), 1252 (m, s), 1092 (w, s), 1062 (s. s), 942 (s, s), 916 (s, s), 824 (w, s), 787 (w,
s), 651 (s, s), 563 (w, s). Elemental analysis % calcd for 3
C H Mn Mo N O Zn ·(C H NO) ): Mn, 2.61; Mo, 27.31; Zn, 4.65. Found: Mn, 2.65;
(
(
6
6
110
2
12 14 58
3
3
7
10
Mo, 26.37; Zn, 4.51. Crystal data for 3. C H Mn Mo N O Zn M = 3484.94, Monoclinic,
6
6
110
2
12 14 58
3,
r
3
I2/a, a = 19.112 (3) Å, b = 19.408 (2) Å, c = 37.690 (5) Å, β = 96.817 (3) °, V = 13882 (3) Å , T
=
100 K, Z = 4, 77133 measured reflections, 12453 unique (R = 0.160), which were used in all
int
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Crystal Growth & Design
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1
2
3
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5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2
2
2
calculations. The final R = 0.143 for 7521 observed data R[F > 2σ(F )] and wR(F ) = 0.370 (all
1
data).
Compound 4. The procedure was identical to the synthesis of 3 but prior to heating, 0.1 mL of
acetic acid is added to the jar. Compound 4 ([NH (CH ) Zn (POM-2) (DMF) (H O) ] )
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
2
3 2
4
3
10
2
2 n
crystallised as orange blocks. Elemental analysis % calcd for 4
C H Mn Mo N O Zn ·(C H NO) ): Mn, 2.89; Mo, 30.21; Zn, 4.58. Found: Mn, 2.85;
(
8
6
142
3
18 17 84
4
3
7
11
Mo, 28.49; Zn, 4.62. Crystal data for 4. C H Mn Mo N O Zn ·(C H NO) M = 5203.76,
86 142
3
18 17 84
4
3
7
4,
r
Monoclinic, I2/a, a = 24.482 (4) Å, b = 24.737 (5) Å, c = 37.321 (8) Å, β = 93.483 (4) °, V =
3
2
2561 (7) Å , T = 100 K, Z = 4, 170624 measured reflections, 25990 unique (R = 0.099), which
int
2
2
were used in all calculations. The final R = 0.048 for 16567 observed data R[F > 2α(F )] and
1
2
wR(F ) = 0.134 (all data).
Compound 5. (TBA) POM-2 (105.5 mg, 0.05 mmol) was added into a 50 mL topꢀscrew jar
3
and dissolved in 10 mL of DMF. Pyridine (8.54 ꢀL, 0.106 mmol) and Zn(NO ) ·6H O (30 mg,
3
2
2
0.1 mmol) were added to the previous solution. The suspension was sonicated for 5 min. A
precipitate was formed and the jar was sealed, placed in a preꢀheated oven at 80 °C and allowed
to heat overnight. Compound 5 ([Zn (POM-2) (DMF) ] ) crystallised as orange blocks.
3
2
12 n
ꢀ1
Selected IR peaks (cm ): 2930 (w, b), 1642 (s, s), 1542 (w, s), 1495 (m, s), 1434 (m ,s), 1417 (w,
s), 1381 (m, s), 1250 (m, s), 1063 (s, s), 939 (s, s), 917 (s, s), 902 (s, s), 828 (w, s) 768 (w, s), 655
(
s, b), 565 (m, s). Elemental analysis % calcd for 5–2DMF (C H Mn Mo N O Zn ): Mn,
66 110 2 12 14 58 3
3.16; Mo, 33.03; Zn, 5.63. Found: Mn, 3.23; Mo, 32.45; Zn, 5.73. Crystal data for 5.
C H Mn Mo N O Zn ·(C H NO) M = 4069.71, Triclinic, Pꢀ1, a = 11.7601 (9) Å, b =
72
124
2
12 16 60
3
3
7
6,
r
14.8366 (11) Å, c = 20.9582 (16) Å, α = 95.541 (2) °, β = 105.037 (2) °, γ = 90.987 (2)°, V =
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Crystal Growth & Design
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3
4
5
6
7
8
9
3
3
511.7 (5) Å , T = 100 K, Z = 1, 67674 measured reflections, 16052 unique (R = 0.029), which
int
2
2
were used in all calculations. The final R = 0.020 for 15080 observed data R[F > 2σ(F )] and
1
2
wR(F ) = 0.050 (all data).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Compound 6. Zn metalated 5,10,15,20ꢀtetra(4ꢀpyridyl)ꢀ21H,23Hꢀporphine (5 mg, 7.5 ꢀmol)
and 10 mL of DMF were added into a 50 mL topꢀscrew jar and the suspension was sonicated for
1
0 min. (TBA) POM-2 (30 mg, 15 ꢀmol) was added to the suspension and the jar sonicated
3
again for 5 min. Finally Cu(NO ) ·2.5H O (31 mg, 1.33 mmol) was added to the suspension and
3
2
2
the jar is sonicated again for another 5 min. Acetic acid (0.1 mL) was added to the jar that was
then placed in a preꢀheated oven at 80 °C and allowed to heat overnight. Compound 6
ꢀ1
(
[Cu(POM-2) (DMF) (Mg(DMF) ) ] ) crystallised as orange blocks. Selected IR peaks (cm ):
2 2 6 2 n
3
389 (w, b), 2930 (w, s), 1647 (s, s), 1498 (w, s), 1436 (m, s), 1417 (m, s), 1384 (s, s), 1252 (m,
s), 1157 (w, s), 1097 (m, s), 1065 (s, s), 937 (s, s), 919 (s, s), 901 (s, s), 827 (w, s), 785 (w, s),
48 (s, s), 563 (m, s). Elemental analysis % calcd for 6
C H CuMg Mn Mo N O ·(C H NO) ): Mn, 2.49; Mo, 26.02; Cu, 1.44; Mg, 1.10. Found:
6
(
7
8
138
2
2
12 18 62
3
7
10
Mn, 2.47; Mo, 24.92; Cu, 1.51; Mg, 1.06. Crystal data for 6.
C H CuMg Mn Mo N O ·(C H NO) M = 4069.71, Triclinic, Pꢀ1, a = 13.338 (5) Å, b =
78
138
2
2
12 18 62
3
7
8,
r
23.136 (8) Å, c = 26.444 (8) Å, α = 87.175 (9)°, β = 85.649 (10) °, γ = 87.712 (12) °, V = 8121
3
(
5) Å , T = 100 K, Z = 2, 19566 measured reflections, 19566 unique (R = 0.0809), which were
int
2
2
2
used in all calculations. The final R = 0.069 for 14855 observed data R[F > 2σ(F )] and wR(F )
1
=
0.177 (all data).
RESULTS AND DISCUSSION
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Crystal Growth & Design
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1
1
1
1
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1
2
2
2
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2
2
2
2
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3
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3
3
3
3
4
4
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4
4
4
4
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5
5
5
5
5
5
5
5
5
6
The principle aim of the work was to synthesise soꢀcalled pillared MOFs by using Mnꢀ
Anderson POMs as bisꢀpyridyl pillars. Given that the MnꢀAnderson POMs have linear
geometries, relatively good rigidities and that they are functionalised by two pyridine units, they
seemed to be good candidates to be used as pillars. We thus used conventional synthetic
conditions to synthesise pillared MOFs, by combining the metal salt, linker and POM in DMF
and applying heat if required, but were unable to isolate any materials with the pillared structural
motif. In fact, we were unable to isolate any materials containing both a POM and a
dicarboxylate linker, which may be a consequence of both being negatively charged (ꢀ3 and ꢀ2,
respectively), instead generating several POMꢀbased Zn and Cu coordination polymers.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Solvothermal syntheses in DMF involving the amidoꢀlinked (TBA) POM-1, Zn(NO ) ·6H O
3
3 2
2
and biphenylꢀ4,4ʹꢀdicarboxylic acid yielded 1 as orange single crystal blocks. The POMs
2+
coordinate to the Zn cations through their pyridyl units to form oneꢀdimensional coordination
polymers, with four DMF solvent molecules completing the octahedral coordination spheres of
2
+
2+
3-
the Zn ions (Figure 2a). The 1:1 ratio of Zn :POM-1 is not charge balanced; heating the
reaction decomposes the DMF and allows the formation of dimethylammonium ions, which can
be identified crystallographically in the solidꢀstate structure of 1, giving the overall formula of
[
(Me NH )Zn(POM-1)(DMF) ] . Although CHN analysis is not sensitive enough to distinguish
2 2 4 n
+
Me NH from the large DMF solvent content of 1, elemental analysis further eliminates the
2
2
+
+
2+
2+
possibility of having an alternative countercation such as Na , K , Mg or additional Zn acting
2+
as a counterion, but suggests coꢀcrystallisation of unreacted biphenylꢀ4,4ʹꢀdicarboxylic with Zn
8
6
as IRMOFꢀ9 in an approximately 2:1 mass ratio. Repeating the reaction without the
dicarboxylic acid did not lead to suitably crystalline material, suggesting it is potentially
templating the reaction, although further work would be required to confirm this possibility.
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Crystal Growth & Design
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When similar reactions are carried out at room temperature, by liquidꢀliquid diffusion of
layered DMF solutions of the individual components, compound 2 results (Figure 2b). In the
+
absence of potential Me NH countercations, 2 crystallises as a twoꢀdimensional sheet structure
2
2
10
11
12
13
14
15
16
17
18
19
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21
22
23
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53
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55
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57
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59
60
with overall formula [Zn (POM-1) (DMF) ] .
3
2
10 n
Figure 2. a) Portion of the solidꢀstate structure of compound 1, showing oneꢀdimensional
+
coordination polymer chains, with DMF solvent molecules and Me NH counterions removed
2
2
for clarity. b) Portion of the solidꢀstate structure of 2, showing the 2D sheet structure. The two
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1
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1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
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5
5
5
5
5
5
5
5
5
6
crystallographically independent POM-1 units are coloured red and green, and DMF ligands and
solvents are removed for clarity. c) The coordination environment of Zn1, which forms part of
the 1D coordination polymer chain. d) The coordination environment of Zn2, which links the
bridging POM-1 anions to the 1D chains to form 2D sheets.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
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9
0
1
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9
0
1
2
3
4
5
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8
9
0
1
2
3
4
5
6
7
8
9
0
2
+
One third of the Zn ions (Zn1) and POM-1 anions assemble through the pyridine units to
generate similar oneꢀdimensional coordination polymers observed in 1. The coordination sphere
of Zn1 is filled by two DMF molecules and terminal oxo groups of two bridging POM-1 anions
which are trans to one another, linking the chains into twoꢀdimensional sheets (Figure 2c). The
2
+
remainder of the Zn ions (Zn2) link the pyridyl nitrogens of the additional bridging POM-1
units to one of the oxo groups of the POM-1 components of the chains, with the rest of the
coordination sphere taken up by four further DMF molecules (Figure 2d).
Although the same POM and Zn salt were used in the assembly of 1 and 2, temperature has
proven to be a determinant parameter on the final structure, suggesting that the anionic nature of
the MnꢀAnderson hybrid makes it easily susceptible to countercation exchange, and so strict
control of the cations present is required for reproducible selfꢀassembly. In the recently reported
Cu(I)ꢀlinked materials, the TBA cations are present in the pores, as a result of the more
8
0
coordinating iodide anions being involved in the linking metal clusters.
The amido linkages in POM-1 induce a step in the linear disposition of the pyridine units, and
so, in order to have a more rigid and linear building block, POM-2 was synthesised, where the
trisꢀhydroxymethyl unit is directly attached to the paraꢀposition of the pyridine donor unit. The
8
5, 87
organic linker was prepared in one step from 4ꢀmethylpyridine,
and the hybrid MnꢀAnderson
prepared by conventional synthesis. Similar attempts were made to isolate pillared MOFs
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Crystal Growth & Design
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2
3
4
5
6
7
8
9
2+
containing dicarboxylic acids and POM-2 linked by Zn , but no materials that could be
characterised by single crystal Xꢀray diffraction resulted. POM-2 also holds three negative
charges, so the dicarboxylate dianions were replaced in solvothermal syntheses by the neutral
zinc complex of 5,10,15,20ꢀtetra(4ꢀpyridyl)porphyrin, which contains multiple potential points
of attachment, to encourage extended framework formation. Two zincꢀlinked coordination
polymers of POM-2 were isolated, compounds 3 and 4, but again no incorporation of the
additional linker was observed.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
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28
29
30
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Compound 3 was isolated from a solvothermal reaction containing Zn(NO ) ·6H O,
3
2
2
(
TBA) POM-2 and zinc 5,10,15,20ꢀtetra(4ꢀpyridyl)ꢀporphine in DMF, and is similar to 2 in both
3
constitution and structure. 3 has an analogous overall formula, [Zn (POM-2) (DMF) ] , and
3
2
10 n
2
+
exhibits similar connectivity, with oneꢀdimensional chains of POM-2 units linked by Zn
cations (Zn1) through coordination to pyridyl nitrogen atoms running along the crystallographic
c axis (Figure 3a). A second set of POM-2 trianions again link the oneꢀdimensional chains
through coordination of terminal oxo units to the Zn1 centres, but the adjacent oxo units from the
two bridging POM-2 units are in a cis configuration (Figure 3b), rather than the trans
configuration seen in 2, with two DMF molecules completing the octahedral coordination sphere.
2
+
The bridging POM-2 units coordinate to the remaining Zn cations (Zn2) through their pyridine
nitrogens, and the Zn2 units coordinate to an oxo group of chain POM-2 trianions as observed in
2, with four further DMF ligands (Figure 3c). The cis arrangement of the bridging POMs around
Zn1 means that each coordination polymer chain is linked to two others at each Zn1 unit, with an
alternating bridging motif at each Zn1 along the coordination polymer chain ensuring that it is
bound to four others (Figure 3d), resulting in an overall threeꢀdimensional connectivity in 3 with
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2
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2
2
2
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3
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3
3
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4
4
4
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4
5
5
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5
5
5
5
5
5
5
6
pores running down the crystallographic a axis (Figure 3e). It is likely that the more rigid
linearity of POM-2 induces this subtle structural change in 3 compared to 2.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
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0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
Figure 3. The solidꢀstate structure of 3. a) Oneꢀdimensional coordination polymer chains formed
between POM-2 and Zn1 linked by additional bridging POM-2 units. DMF ligands and solvents
removed for clarity. b) The coordination sphere of the Zn1, which forms the chains. c) The
coordination sphere of Zn2, which links the chains via the bridging POMꢀ2 anion. d) The
different bridging directions around adjacent Zn1 cations that generate a threeꢀdimensional
packing structure. e) Extended packing structure of 3 showing channels that run along the
crystallographic a axis. DMF ligands and solvents removed for clarity.
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Crystal Growth & Design
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Compound 4 was isolated during attempts to incorporate the zinc porphyrin coꢀligand into
framework structures, in this case by modifying the solvothermal synthetic protocol used for 3
by addition of 0.1 mL acetic acid. 4 is comprised of three crystallographically independent half
POMs and two independent Zn centres, with the overall formula [(Me NH )Zn (POM-
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
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31
32
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34
35
36
37
38
39
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44
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48
49
50
51
52
53
54
55
56
57
58
59
60
2
2
4
2) (DMF) (H O) ] . The structure is based on “zigzag”ꢀlike coordination polymer chains, where
3
10
2
2 n
2
+
one of the crystallographically independent Zn cations (Zn1) coordinates to two
crystallographically independent POM-2 anions through their pyridine groups in a cis
configuration (Figure 4a). The chains face each other in a symmetrical fashion, related by a C2
axis, with two further POMs (coloured purple and red in Figure 4a) linking them together. The
red POM forms bonds to Zn1 ions (Figure 4b) of adjacent zigzag chains through coordination to
its terminal oxo centres. The third crystallographically independent POM-2 (purple in Figure 4a)
bridges the POMs in the zigzag chains by coordinating to Zn2 cations (Figure 4c) through its
pyridyl units, while the Zn2 centres coordinate to oxo units of the zigzag chain POMs.
Overall, the octahedral Zn1 cations bridge two pyridyl units of two different POMs of one
zigzag chain in a cis arrangement, a terminal oxo of another zigzag chain POM and a terminal
oxo unit of a bridging POM in a trans arrangement, with two DMF molecules completing the
coordination sphere. The Zn2 cations coordinate to the pyridyl nitrogen of one bridging POM, a
terminal oxo of a zigzag chain POM, three DMF molecules and one water molecule. The red
POMs form further zigzag coordination polymer chains in the third dimension (Figure 4d),
which link the sheets shown in Figure 4a into a complex threeꢀdimensional network. The result is
a threeꢀdimensional structure with significant pores of approximately 1.5 nm diameter that run
+
along the crystallographic a axis (Figure 4e). The Me NH cation is disordered across two 0.25
2
2
occupied sites in the asymmetric unit, while elemental analysis showed no presence of alkali
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1
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2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
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4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
2+
metals or additional Zn ions, as was the case for 1 (see Supporting Information, Section S2).
2
+
We postulate that the addition of acetic acid to the mixture may induce competition for the Zn
ions that link the anionic POM-2 molecules, slowing down selfꢀassembly and crystallisation, and
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thus allowing sufficient Me NH cations to form through thermal decomposition of DMF and
2
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produce the alternative structure.
Figure 4. The solidꢀstate structure of 4. a) The connectivity between neighbouring “zigzag”
coordination polymer chains (two crystallographically identical chains are coloured separately
green and yellow as a guide) through bridging POM-2 anions (purple) to form 2D sheets. DMF
ligands and solvents removed for clarity. b) The coordination sphere of the Zn1, which forms the
zigzag chains. c) The coordination sphere of Zn2, which links the chains via the bridging POM-
2
anion. d) The red POM-2 anions shown in part a) are themselves components of zigzag chains
which extend into the third dimension, and are crystallographically identical to the other chains.
DMF ligands and solvents removed for clarity. e) Extended packing structure of 4 showing
channels that run along the crystallographic a axis. DMF ligands and solvents removed for
clarity.
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Both 3 and 4 are threeꢀdimensional coordination polymers with potential porosities in the form
of oneꢀdimensional channels along their crystallographic a axes. Analysis of the structures with
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the SQUEEZE function within PLATON calculated solvent accessible voids of 29% and 30%
of the unit cells of 3 and 4, respectively. Unfortunately, both compounds show a complete loss of
stability and crystallinity when dried: N adsorption isotherms collected at 77 K show no uptake
2
of gas, while PXRD patterns indicate a significant loss of crystallinity. The prevalence of
2
+
multiple DMF ligands coordinated to the Zn centres may explain this instability under drying,
as they are key components of the materials, and significant mass loss is observed at low
temperatures by thermogravimetric analysis (see Supporting Information, Section S3). It may
also be a possibility that small amounts of 4 can crystallise alongside 3, but this cannot be
examined due to the rapid loss of crystallinity upon drying.
As attempts to replicate the synthesis of 4 were unsuccessful, the influence of other
coordinating ligands in synthetic mixtures was investigated by addition of pyridine, to mimic the
tetrapyridyl porphyrin. Addition of competing ligands to MOF synthesis is commonly known as
8
9
90ꢀ92
coordination modulation, and has been applied both to downsizing MOF crystal size
also to enhancing the syntheses of MOFs linked by early transition metals such as zirconium.
Solvothermal reaction of (TBA) POM-2, Zn(NO ) ·6H O and pyridine in DMF resulted in the
and
93,94
3
3 2
2
isolation of another coordination polymer, 5, which has general formula [Zn (POM-2) (DMF) ]
3
2
12
and is closely related to both 2 and 3 (Figure 5). The material consists of oneꢀdimensional chains
2
+
of POM-2 anions connected by Zn cations (Zn1), with four DMF molecules completing the
coordination sphere. The chains are linked into twoꢀdimensional sheets by bridging POM-2
2+
anions that bond to further Zn ions (Zn2), which themselves coordinate to terminal oxo units of
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POM-2 anions to connect adjacent chains. Four DMF ligands complete the coordination spheres
of the Zn2 centres. The key structural difference between 5 and both 2 and 3 is the lack of
coordination from the Zn1 ions in the oneꢀdimensional chains to the oxo units of the bridging
POM-2 anions, with DMF molecules occupying these positions around Zn1. The structure is
densely packed, with multiple wellꢀordered DMF solvent molecules occupying interstitial
spaces.
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Figure 5. Representation of the solidꢀstate structure of 5, showing the oneꢀdimensional chains of
POM-2 anions in red and the bridging POM-2 anions in green. DMF solvent molecules
removed for clarity.
The isolation of 5 was unexpected given previous results, and demonstrates another potential
synthetic variable in the selfꢀassembly of these coordination polymers. It is possible pyridine is
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acting either as a template or a modulator during synthesis – the same could apply to the
tetrapyridyl porphyrin during the assembly of 3 and 4 – so the presence of molecules intended as
coꢀligands could influence the selfꢀassembly of structures in which they are not included.
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2+
It is clear from the coordination polymers formed with connecting Zn cations that, despite
the deliberate introduction of coordinating pyridyl units into the hybrid MnꢀAnderson clusters,
coordination of the metal centres to the terminal oxo units is still prevalent. Whilst this may seem
unpredictable, we have observed a common structural feature in 2, 3, and 4: a “square” motif
2
+
formed by coordination of two POMs to two Zn ions through pyridyl nitrogens and oxo units
Figure 6). The cis coordination of one oxo unit from one POM and one pyridyl unit from an
(
2
+
adjacent POM by the Zn centres seems to be favourable regardless of the nature of the hybrid
MnꢀAnderson, and may be a significant structural driving force in these systems.
2
+
Figure 6. Common square motif formed by two hybrid POMs and two Zn cations in the solidꢀ
state structures of a) 2, b) 3, and c) 4.
In an attempt to disrupt these interactions, other transition metals have been examined for selfꢀ
2
+
assembly with POM-2, but not POMꢀ1. Solvothermal syntheses with Cu salts generally did not
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yield crystals of suitable quality for analysis, but in one case, where (TBA) POM-2,
3
Cu(NO ) ·2.5H O and zinc 5,10,15,20ꢀtetra(4ꢀpyridyl)ꢀporphine were heated in DMF,
3 2
2
compound 6 was isolated and found to be a square grid structure (Figure 7a) with chargeꢀ
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2+
balancing [M(DMF) ] cations. The twoꢀdimensional squareꢀgrid motif shows that hybrid
6
POMs clearly have the potential to form wellꢀordered coordination polymer structures with some
level of control over selfꢀassembly – no unwanted coordination to the terminal oxo units of
2
+
POM-2 occurs in 6, with the remainder of the coordination sphere of the Cu cations occupied
by two DMF ligands (Figure 7b).
2
+
Figure 7. a) Solidꢀstate packing of the square grid formed by POM-2 and Cu cations in 6.
Counterions, DMF ligands and solvents removed for clarity. b) The coordination sphere of the
2
+
2+
Cu ion in 6 showing coordination to two additional DMF ligands, with adjacent [Mg(DMF) ]
6
counter cations displayed.
2+
2+
Crystallographically, M refines well as Mg both in terms of electron density and geometry,
although it was not deliberately incorporated into the initial synthesis, and the composition of 6
has been confirmed by elemental analysis to be [Cu(POM-2) (DMF) (Mg(DMF) ) ] . The
2
2
6 2 n
2+
presence of adventitious Mg suggests an impurity in starting materials or contamination in
2
+
equipment: less than 750 ꢀg of Mg would be required for 6 to crystallise in 100% yield from
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the reaction at the scale utilised. Attempts to reproduce the synthesis of 6 with deliberate addition
2
+
of Mg were unsuccessful, further illustrating the need to control the presence of cations in the
assembly of this class of material.
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CONCLUSIONS
We have described the solidꢀstate structures of a number of coordination polymers formed
through selfꢀassembly of pyridylꢀfunctionalised MnꢀAnderson hybrid polyoxometalates with
transition metal ions. Whilst the use of hybrid POMs seems like an appropriate strategy for
rational design and isolation of POMꢀcontaining MOFs of specific topologies, our study has
revealed a number of design considerations. (i) As most POMs are anionic, their incorporation
into MOF structures containing other anionic ligands may be disfavoured, possibly requiring
high valent metal cations to do so. (ii) The addition of coꢀligands into syntheses may induce
templation, even when they are not incorporated into the final structure, although further
experiments would be required to investigate this. (iii) Competing ligands, such as acetic acid
and pyridine, may also influence the product structure through templating or coordination
modulation. (iv) The control of cation content in syntheses containing hybrid POMs is vital, as
simple ion metathesis may occur and result in isolation of unexpected materials. (v) Control of
heating time is required, as the formation of small organic cations from formamide solvent
decomposition can influence product composition, as in the isolation of 1 and 2. (vi) Even with
deliberate grafting of metal binding units onto POMs, the coordination of metal centres to
terminal oxo units is still possible, with the common square structural motif seen in 2, 3, and 4 a
2
+
potential driving force for formation of materials linked by Zn . As the pyridine donors are
softer bases than the terminal oxo groups, the use of softer metal ions may offer more structural
2+
control, for example the square grid linked by Cu and the very recent example of threeꢀ
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+ 80
dimensional frameworks of POM-2 linked by Cu . It is clear that hybrid POMS can assemble
into a diverse range of complex coordination polymer structures, and we expect these synthetic
guidelines will assist in future efforts to control the selfꢀassembly of hybrid polyoxometalates
into extended porous networks and enhance the reproducibility of their syntheses.
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ASSOCIATED CONTENT
Crystallographic data, elemental analysis, IR spectra and thermogravimetric analysis data. This
material is available free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*ross.forgan@glasgow.ac.uk
Author Contributions
The manuscript was written through contributions of all authors. All authors have given approval
to the final version of the manuscript.
Funding Sources
RSF thanks the Royal Society for receipt of a University Research Fellowship. RSF and FJY
thank the University of Glasgow for funding.
ACKNOWLEDGMENT
We thank Prof Lee Cronin, University of Glasgow, for diffractometer access and useful
discussions. We thank the EPSRC UK National Crystallography Service at the University of
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Southampton for the collection of the crystallographic data for 1. CCDC 1539320ꢀ1539325 and
1
539576 contain the supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif..
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3 2 11
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Enhanced Water Oxidation Using Rb [Ru (bpy) ] [{Ru O (OH) (H O) }(γꢀSiW O ) ] Film
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Modified Electrodes Inorg. Chem. 2014, 53, 7561.
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