Unique Copper-Organic Networks Self-Assembled from 1,3,5-Triaza-7-Phosphaadamantane and Its Oxide: Synthesis, Structural Features, and Magnetic and Catalytic Properties

Article abstract of DOI:10.1021/acs.cgd.7b01581

Three new coordination compounds, namely, a zero-dimensonal dicopper(II) complex [Cu₂(μ-MeCOO)₄(MeOH)₂](PTA = O)₂ (1), a three-dimensional (3D) copper(II)-organic framework [Cu₃(μ-MeCOO)₆(μ₃-PTA=O)]_n·3.5nMeCN (2), and a mixed-valence copper(I/II) one-dimensional (1D) coordination polymer [Cu₃(μ-MeCOO)₄(MeCOO)(μ-PTA)₂(PTA)]_n (3), were self-assembled from copper(II) acetate and cage-like aminophosphine 1,3,5-triaza-7-phosphaadamantane (PTA) or its P-oxide (PTA=O). The obtained products were isolated as air-stable crystalline solids and characterized by IR and electron paramagnetic resonance spectroscopy, thermogravimetric and elemental analysis, as well as single crystal X-ray diffraction. Although all compounds bear dicopper(II) paddle-wheel tetraacetate [Cu₂(μ-MeCOO)₄] blocks, they are arranged into very distinct metal-organic architectures. The structure of 2 reveals an intricate 3D metal-organic framework (MOF) driven by the μ₃-PTA=O spacers acting in an unusual N,N,O-tridentate mode, whereas the compound 3 discloses an infinite 1D wave-like metal-organic chain with the dicopper(II) [Cu₂(μ-MeCOO)₄] and monocopper(I) [Cu(PTA)(MeCOO)] blocks being interlinked by the μ-PTA linkers acting in an N,P-bidentate mode. Topological analysis of underlying nets was performed, revealing a decorated uninodal 3-connected framework with the ths topology in 2 and a uninodal 2-connected chain with the 2C1 topology in 3. Compounds 2 and 3 broaden a still very limited family of MOFs or coordination polymers assembled from PTA or its P-oxide building blocks, also showing that PTA can be applied for the generation of unusual mixed-valence copper(I/II) derivatives. Besides, 2 represents the first example of a copper-containing 3D MOF that is driven by PTA=O or any other PTA-derived block. Magnetic properties of 1-3 were investigated, modeled, and discussed in detail, resulting in the exchange coupling parameters (J = -310, -320 cm^-1) that indicate a strong antiferromagnetic interaction within the dicopper(II) paddle-wheel blocks. Moreover, compounds 1 and 2 show a notable catecholase activity in the aerobic oxidation of 3,5-di-tert-butyl-catechol to 3,5-di-tert-butyl-o-benzoquinone; turnover frequency values of up to 81 min^-1 were attained.

Full text of DOI:10.1021/acs.cgd.7b01581

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Unique Copper-Organic Networks Self-Assembled from 1,3,5-
Triaza-7-Phosphaadamantane and its Oxide: Synthesis,
Structural Features, Magnetic and Catalytic Properties
Ewelina I. Sliwa, Dmytro S. Nesterov, Julia Klak, Piotr Jakimowicz, Alexandr M. Kirillov, and Piotr Smole#ski
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01581 • Publication Date (Web): 03 Apr 2018
Downloaded from http://pubs.acs.org on April 3, 2018
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Unique Copper-Organic Networks Self-Assembled from 1,3,5-Triaza-7-
Phosphaadamantane and its Oxide: Synthesis, Structural Features, Magnetic and
Catalytic Properties
†
‡
†
§
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Ewelina I. Śliwa, Dmytro S. Nesterov, Julia Kłak, Piotr Jakimowicz, Alexander M.
*,‡
*,†
Kirillov, and Piotr Smoleński
†
Faculty of Chemistry, University of Wroclaw, 50ꢀ383, ul. F. JoliotꢀCurie 14, Wroclaw, Poland;
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco
Pais, 1049ꢀ001 Lisbon, Portugal;
‡
§
Faculty of Biotechnology, University of Wroclaw, 50ꢀ383, ul. F. JoliotꢀCurie 14a, Wroclaw, Poland.
*
To whom correspondence should be addressed. Eꢀmail: piotr.smolenski@chem.uni.wroc.pl (P.S.),
kirillov@tecnico.ulisboa.pt (A.M.K.).
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ABSTRACT
Three new coordination compounds, namely a 0D dicopper(II) complex [Cu
MeCOO) (MeOH) ](PTA=O) (1), a 3D copper(II)ꢀorganic framework [Cu (µꢀMeCOO)
PTA=O)] ·3.5nMeCN (2), and a mixedꢀvalence copper(I/II) 1D coordination polymer [Cu
MeCOO) (MeCOO)(µꢀPTA) (PTA)] (3), were selfꢀassembled from copper(II) acetate and
2
(µꢀ
4
2
2
3
6
(ꢀ
3
ꢀ
n
3
(µꢀ
4
2
n
cageꢀlike aminophosphine 1,3,5ꢀtriazaꢀ7ꢀphosphaadamantane (PTA) or its Pꢀoxide (PTA=O).
The obtained products were isolated as airꢀstable crystalline solids and characterized by IR
and EPR spectroscopy, thermogravimetric and elemental analysis, as well as single crystal Xꢀ
0
1
2
3
4
5
6
7
8
9
0
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2
3
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0
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2
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0
ray diffraction. Although all compounds bear dicopper(II) paddleꢀwheel tetraacetate [Cu
MeCOO) ] blocks, they are arranged into very distinct metalꢀorganic architectures. The
structure of 2 reveals an intricate 3D metalꢀorganic framework (MOF) driven by the µ
PTA=O spacers acting in an unusual N,N,Oꢀtridentate mode, whereas the compound 3
discloses an infinite 1D waveꢀlike metalꢀorganic chain with the dicopper(II) [Cu (µꢀ
MeCOO) ] and monocopper(I) [Cu(PTA)(MeCOO)] blocks being interlinked by the µꢀPTA
2
(µꢀ
4
3
ꢀ
2
4
linkers acting in an N,Pꢀbidentate mode. Topological analysis of underlying nets was
performed, revealing a decorated uninodal 3ꢀconnected framework with the ths topology in 2
and a uninodal 2ꢀconnected chain with the 2C1 topology in 3. Compounds 2 and 3 broaden a
still very limited family of MOFs or coordination polymers assembled from PTA or its Pꢀ
oxide building blocks, also showing that PTA can be applied for the generation of unusual
mixedꢀvalence copper(I/II) derivatives. Besides, 2 represents the first example of a copperꢀ
containing 3D MOF that is driven by PTA=O or any other PTAꢀderived block. Magnetic
properties of 1–3 were investigated, modelled, and discussed in detail, resulting in the
–1
exchange coupling parameters (J = –310, –320 cm ) that indicate a strong antiferromagnetic
interaction within the dicopper(II) paddleꢀwheel blocks. Moreover, the compounds 1 and 2
show a notable catecholase activity in the aerobic oxidation of 3,5ꢀdiꢀtertꢀbutylꢀcatechol to
–
1
3
,5ꢀdiꢀtertꢀbutylꢀoꢀbenzoquinone; turnover frequency values of up to 81 min were attained.
Introduction
Synthesis of novel copperꢀbased coordination compounds using P,Nꢁ and N,Oꢀ
donating building blocks has become a popular research direction, especially aiming at the
generation of coordination polymers (CPs) that possess a wide structural diversity and notable
1
ꢀ6
magnetic, catalytic, optical, hostꢀguest, and therapeutic properties. Many coordination
polymers are often prepared by complicated and multistage synthetic procedures, or require
the use of very complex building blocks. In this regard, 1,3,5ꢀtriazaꢀ7ꢀphosphaadamantane
(
PTA) and its Pꢀoxide derivative (PTA=O) represent a very interesting class of cageꢀlike P,Nꢀ
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or N,Oꢀdonor building blocks on account of their stability, aqueous solubility, and rich
7ꢀ19
coordination chemistry.
However, the application of such building blocks for the synthesis
of functional coordination polymers is much less explored if compared with the conventional
aromatic polycarboxylate or Nꢀheterocyclic ligands.
On the other hand, copper is a bioessential element that is present in all organisms
living in oxygenꢀrich environments. In particular, catechol oxidase is a type III active site
1
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20
metalloprotein that contains copper and shows catecholase activity. In nature, such
metalloproteins are very efficient catalysts for the oxidation of oꢀdiphenols to the
2
1,22
corresponding oꢀdiquinones via the reduction of molecular oxygen to water.
studies on the model compounds as bioinspired catalysts with catecholase activity are
Therefore,
2
3,24
promising for the evolution of new catalytic systems.
Despite a good number of copper
complexes that were tested as catalysts for the oxidation of catechols, catalytic systems based
25ꢀ27
on copper coordination polymers are still scant.
Following our interest in the selfꢀassembly synthesis of copper coordination
compounds driven by PTA or derived building blocks, we have reported some unique mixedꢀ
valence copper(I/II) derivatives, namely a tetranuclear complex [Cu
4
I
4
(µꢀN
3
)
2
(N
3
)
4
(µꢀ
(µꢀ
9
mPTA)
2
2
(mPTA) ]·2H
2
O
and a 1D coordination polymer [Cu (µꢀHCOO) (HCOO)
3 2
3
1
0
PTA) (PTA)] ·nH O, which are driven by Nꢁmethylꢀ1,3,5ꢀtriazaꢀ7ꢀphosphaadamantane(1+)
3
n
2
(mPTA) or PTA blocks, respectively.
Inspired by these results and aiming at extending the series of such compounds to
other PTAꢀbased building blocks and to more complex structures including 3D metalꢀorganic
frameworks, we have attempted a number of selfꢀassembly reactions using dicopper(II)
paddleꢀwheel tetraacetate blocks and cageꢀlike PTA=O or PTA spacers. As a result, three
novel compounds were generated. Their structures range from a 0D dicopper(II) compound
[
Cu
MeCOO)
polymer [Cu
2
(µꢀMeCOO)
(ꢀ ꢀPTA=O)]
(µꢀMeCOO)
4
(MeOH)
·3.5nMeCN (2), and a mixedꢀvalence copper(I/II) 1D coordination
(MeCOO)(µꢀPTA) (PTA)] (3). Hence, the present work describes
2 2 3
](PTA=O) (1) to a 3D copper(II)ꢀorganic framework [Cu (µꢀ
6
3
n
3
4
2
n
the selfꢀassembly synthesis, full characterization, structural and topological features, thermal
and magnetic properties, as well as catecholase catalytic activity of these compounds. It
should be highlighted that compound 2 represents the first 3D copperꢀbased MOF driven by
any cageꢀlike derivative of PTA, as attested by a search of the Cambridge Structural
Database.
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Experimental
Materials and Methods. Syntheses of 1 and 2 were performed in air, while 3 was
obtained under dry dinitrogen, using standard Schlenk techniques. All reagents and solvents
were obtained from commercial sources and used as received, except from 1,3,5ꢀtriazaꢀ7ꢀ
phosphaadamantane (PTA) and 1,3,5ꢀtriazaꢀ7ꢀphosphaadamantaneꢀ7ꢀoxide (PTA=O) that
2
8,29
–1
were synthesized in accord with literature methods.
The infrared spectra (4000−400 cm )
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0
were recorded on a Bruker Vertex 70 FTIR instrument in KBr pellets. Elemental analyses
were performed on a CHNS Vario EL CUBE apparatus. Thermal analyses were run on a TGꢀ
DTA Setaram SETSYS 16/18 equipment using 10.694 (1), 11.358 (2), or 9.500 (3) mg of the
2
compound sample (N atmosphere, heating rate 10 °C/min). Powder Xꢀray analyses were
performed with a Bruker D8 ADVANCE diffractometer using a Cu Kα radiation (λ = 1.5418
Å) filtered with Ni. The diffractograms were recorded with a step size of 2θ = 0.024° to
0
.048° over the range of 2θ = 5–60° and ratio 0.5. The calculated patterns were obtained from
the singleꢀcrystal Xꢀray data using the MERCURY CSD 3.9 package. It should be noted that
the compounds 1ꢀ3 are soluble in water and their single crystals are sensitive to the presence
2
of moisture in air, can adsorb additional H O molecules from air, and/or can lose solvent
molecules during storage. Hence, in some cases (in particular, for 2), the PXRD data of bulk
samples do not exactly match the theoretical plots calculated from the singleꢀcrystal Xꢀray
data. Catecholase activity studies were performed using an Agilent Cary 8454 UVꢀVisible
Spectrophotometer with Agilent 89090A Peltier temperature controller with magnetic stirrer
controller, and 845x UVꢀVis System.
Synthesis and Analytical Data
[
Cu
anhydrous [Cu(MeCOO)
mmol) in methanol (100.0 mL). The reaction mixture was stirred at room temperature (r.t.,
25 ºC) for 30 min and then filtered off. The filtrate was left to evaporate in air for several
days at r.t., producing blue Xꢀray quality single crystals. These were dried in air to furnish 1
in 55% yield, based on PTA=O. Compound 1 is soluble in H O, DMSO, MeOH and warm
MeCN. Anal. Calcd for C22 (MW 773.5), %: C 34.16; H 5.68; N 10.85; found,
: C 34.15; H 5.73; N 10.86. IR (KBr, cm ): 3435 (s br.) and 3135 (s br.) ν(OH), 2961 (m),
927 (m), 2831 (m), 1610 (vs) and 1421 (vs) νas(COO), 1364 (m) ν (COO), 1297 (s), 1282
(vs), 1238 (s), 1156 (vs), 1097 (m), 1026 (s), 1007 (s), 978 (vs), 943 (w), 912 (s), 818 (m),
14 (m), 786 (w), 739 (m), 683 (s), 632 (m), 580 (s), and 453 (m). TGꢀDTA (N , 10
2
(µ-MeCOO)
4
(MeOH)
2 2
](PTA=O) (1). To a methanol solution (50.0 mL) of
2 2
] (182 mg, 0.50 mmol) was added a solution of PTA=O (179 mg, 1
~
2
H
2 6 12 2
44Cu N O P
−1
%
2
s
8
2
°C/min):110−160 °C (−2MeOH, ∆m: 8.35% exptl., 8.28% calcd.), >200 °C (dec.).
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[
Cu (µ-MeCOO) (µ -PTA=O)] ·3.5nMeCN (2). Solid PTA=O (352 mg, 2 mmol)
3 6 3 n
2 2
was added to an acetonitrile solution (50.0 mL) of anhydrous [Cu(MeCOO) ] (182 mg, 0.50
mmol). The obtained mixture was refluxed for 1 h and then filtered off. The filtrate was left to
slowly evaporate at ~4 ºC for several days, producing green Xꢀray quality single crystals of 2.
If these crystals are dried and kept in air,
Cu (MeCOO) (PTA=O)] ꢁnH O (2’) is produced in 46% yield, based on the copper(II)
acetate. Compound 2 is soluble in H O, MeOH, MeCN, and DMSO. Anal. Calcd for
O (MW 736.1), %: C 29.60, H 4.40, N 6.00; found, %: C 29.37, H 4.38,
a
monohydrate derivative
[
3
6
n
2
1
1
1
1
1
1
1
1
1
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2
18 3 3 2
C H30Cu N O13P·H
–1
N 5.71. IR (KBr, cm ): 3435 (w br.) ν(H
(COO), 1299 (m), 1277 (w), 1221 (w), 1182 (m), 1085 (w), 1003 (w), 987 (w), 966 (m), 905
(vw), 795 (w), 684 (s), 627 (w), and 605 (w). TGꢀDTA (N , 10 K/min): 50–190 °C (–1.5H O,
m: % 3.51 exptl., 3.63 % calcd.), >190 °C (dec.).
Cu (µ-MeCOO) (MeCOO)(µ-PTA) (PTA)]
mg, 5 mmol) was added to an acetonitrile solution (50.0 mL) of anhydrous [Cu(MeCOO)
182 mg, 0.5 mmol). The reaction mixture was stirred at r.t. overnight, resulting in a gradual
2
O), 1620 (vs) and 1437 (vs) νas(COO), 1347 (w)
ν
s
2
2
∆
[
3
4
2
n
(3). An excess of fine Cu powder (317
2 2
]
(
color change from green to colorless, and then was filtered off. Solid PTA (321 mg, 2 mmol)
was added to the obtained filtrate. The resulting mixture was refluxed under dinitrogen for 15
min and then filtered off in air. The filtrate was left to evaporate for several days in air at r.t.,
resulting in green Xꢀray quality single crystals. These were collected and dried in air to
furnish 3 in 10% yield, based on the copper(II) acetate. Compound 3 is soluble in H
2
O,
sparingly soluble in warm DMSO (slow decomposition occurs), and insoluble in MeOH and
MeCN. Anal. Calcd for C28
H
51Cu
3
N
9
O
10
P
3
(MW 957.3), %: C 35.30; H 5.28; N 13.24; found,
–1
%
: C 35.13; H 5.37; N 13.17. IR (KBr, cm ): 2968 (m), 2936 (m), 1616 (vs) and 1426 (vs)
ν
as(COO), 1372 (s) and 1349 (s) ν
015 (vs), 1000 (m), 992 (m), 972 (vs), 957 (s), 949 (vs), 887 (w), 810 (m), 799 (s), 763 (m),
45 (m), 681 (s), 629 (w), 608 (s), 582 (s), and 564 (m). TGꢀDTA (N , 10 °C/min): >190 °C
s
(COO), 1289 (s), 1237 (s), 1100 (m), 1050 (m), 1036 (m),
1
7
2
(dec.).
Refinement Details for X-ray Analysis. The diffraction data for 1–3 were collected
using an Oxford Xcalibur2 KM4 diffractometer with graphiteꢀmonochromated MoꢀKα
radiation. The collection and integration of crystal data were performed with the CrysAlis
30,31
CCD, CrysAlis RED and CrysAlisPro systems at 100(2) K.
The absorption correction was
3
1
executed with the CrysAlis RED and CrysAlisPro software. The structure was solved by
2
direct methods and refined by fullꢀmatrix leastꢀsquares methods on F with the SHELXLꢀ
32
2
016/6 program package. The nonꢀhydrogen atoms were refined anisotropically, except of
the C100, C101, C102, C103, N100 and N101 atoms of acetonitrile solvent in 2. Three of five
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acetonitrile molecules in 2 (C104, C105, N102; C106, C107, N103 and C108, C109, N104)
were considered to possess 0.5 sites occupation, forming a disordered model (Figure S2). All
hydrogen atoms were placed at calculated positions and refined using a riding model with Uiso
=
nUeq (n = 1.2 for H atoms of methylene groups and n = 1.5 for other H atoms), except of H1
atom in 1, which was located in the difference map and refined.
Crystal data for 1: C22
H
44Cu
2
N
6
O
12
P
2
, M = 773.65, a = 10.9387(4) Å, b = 9.5736(6)
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1
2
3
4
5
6
7
8
9
0
3
Å, c = 14.7979(5) Å, α = 90°, β = 90.604(4)°, γ = 90°, V = 1549.59(12) Å , T = 100(2) K,
space group I2/m, Z = 2, 12949 reflections measured, 4054 independent reflections (Rint
=
2
0.0528). The final R
1
values were 0.0497 (I > 2σ(I)). The final wR(F ) values were 0.1207 (all
2
3 6.50
data). The goodness of fit on F was 1.036. Crystal data for 2: C25H40.5Cu N O13P, M =
861.73, a = 15.154(3) Å, b = 25.427(3) Å, c = 19.928(3) Å, α = 90°, β = 104.366(17)°, γ =
3
9
0°, V = 7438(2) Å , T = 100(2) K, space group C2/c, Z = 8, 16682 reflections measured,
8382 independent reflections (Rint = 0.0460). The final R
1
values were 0.0673 (I > 2σ(I)). The
2
2
final wR(F ) values were 0.1746 (all data). The goodness of fit on F was 1.030. Crystal data
for 3: C H Cu N O P , M = 957.30, a = 8.0542(6) Å, b = 25.5933(13) Å, c = 9.6214(6) Å,
2
8
51
3
9
10 3
3
α = 90°, β = 113.794(8)°, γ = 90°, V = 1814.7(2) Å , T = 100(2) K, space group P21/m, Z = 2,
1
1
6751 reflections measured, 5955 independent reflections (Rint = 0.0852). The final R values
2
were 0.0521 (I > 2σ(I)). The final wR(F ) values were 0.1046 (all data). The goodness of fit
2
on F was 0.811.
CCDC 1541175 (1), 1541176 (2), 1541177 (3) contain the supplementary
crystallographic data. Ellipsoid plots for 1–3 are given in Figures S1–S3, respectively (SI).
Magnetic and EPR Studies. The magnetization of powdered samples 1–3 was
measured over the temperature range 1.8–300 K using a Quantum Design SQUID – based
MPMSXL–5ꢀtype magnetometer. The superconducting magnet was generally operated at a
field strength ranging from 0 to 5 T. Measurements were made at magnetic field 0.5 T. The
SQUID magnetometer was calibrated with the palladium rod sample. Corrections are based
D
on subtracting the sample – holder signal and the contribution of χ was estimated from the
33
Pascal’s constants. EPR spectra of powdered samples 1–3 were recorded at room
temperature and 77 K on a Bruker ELEXSYS E 500 CWꢀEPR spectrometer operating at Xꢀ
band frequency and equipped with an ER 036TM NMR Teslameter and E41 FC frequency
counter.
Catecholase Activity Studies. The catecholase activity of the copper(II) compounds
was evaluated in the oxidation of 3,5ꢀdiꢀtertꢀbutylꢀcatechol (3,5ꢀDTBC) as a model substrate
to give the corresponding quinone, 3,5ꢀdiꢀtertꢀbutylꢀoꢀbenzoquinone (3,5ꢀDTBQ). The
experiments were performed under aerobic conditions at constant stirring and temperature 25
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2
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°
C, and monitored by a contact thermometer dipped into the reaction solution. Measurements
were made in a 1 cm path length quartz cuvette. In a typical test, 1.0 mL MeOH solution of
ꢀ5
ꢀ5
catalyst (6.53×10 M for 1, 6.50×10 M for 2) was treated with 0.01–2.00 mL MeOH
ꢀ5
ꢀ2
ꢀ5
ꢀ2
solution of 3,5ꢀDTBC (6.77×10 –1.35×10 M for 1; 6.67×10 –1.33×10 M for 2) in air at
o
2
5 C. Due to a lack of solubility of 3 in MeOH, the catalytic activity of this compound was
not investigated. The absorbance was measured as a function of time, over the first 5 min, at
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
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
ꢀ1
ꢀ1
3
90 nm (ε=1734.49 M cm ) immediately after the addition of catalyst. For comparative
ꢀ5
2
purposes, Cu(MeCOO) (1.0 mL of MeOH solution, 6.80×10 M) and a freshly prepared
ꢀ5
mixture of Cu(MeCOO)
2
and PTA=O (1.0 mL of MeOH solution, 6.23×10 M) were also
ꢀ
tested as reference catalysts in the oxidation of 3,5ꢀDTBC (0.03–1.80 mL in MeOH, 1.99×10
4
ꢀ2
ꢀ4
ꢀ2
–1.19×10 M for copper(II) acetate; 0.02–2.00 mL in MeOH, 1.33×10 – 1.33×10 M for
copper(II) acetate and PTA=O in 1:1 molar ratio). Control experiments were carried out under
typical reaction conditions but in the absence of copper(II) catalyst, and showed no
conversion of 3,5ꢀDTBC to 3,5ꢀDTBQ.
Results and Discussion
Self-assembly Synthesis and Characterization. Reaction of copper(II) acetate with
PTA=O in MeOH medium leads to the selfꢀassembly of a discrete dicopper(II) complex
2 4 2 2
[Cu (µꢀMeCOO) (MeOH) ](PTA=O) (1) (Scheme 1). A resembling reaction but using
acetonitrile instead of methanol as a solvent resulted in the generation of a 3D copper(II)
MOF [Cu (µꢀMeCOO) (µ ꢀPTA=O)] ꢁ3.5nMeCN (2). Interestingly, the µ ꢀPTA=O spacer in
3
6
3
n
3
2
is connected to axial positions of metal centers (Scheme 1), whereas in 1 the axial positions
of copper centers are blocked by methanol molecules; as a result, PTA=O remains
uncoordinated. A different selfꢀassembly reaction in MeCN using both copper(II) acetate and
metallic copper(0) powder as metal sources and PTA as a building block furnished a mixedꢀ
3 4 2 n
valence Cu(II)/Cu(I) 1D coordination polymer [Cu (µꢀMeCOO) (MeCOO)(µꢀPTA) (PTA)]
(3) (Scheme 1), wherein PTA moieties act as both P,Nꢀlinkers and terminal Pꢀligands. All the
compounds 1–3 were isolated as airꢀstable crystalline solids, their molecular structures were
established by single crystal Xꢀray diffraction and further supported by elemental analysis,
TGA, IR and EPR spectroscopy.
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1
1
1
1
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1
1
1
2
2
2
2
2
2
2
2
2
2
3
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3
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6
N
N
N
N
Me
O
N
Cu powder, PTA
O
N
N
N
O
O
Me
O
P
P
MeCN, N , reflux
2
P
N
Me
Cu
Cu
O
O
O
O
P
Cu
Cu
O
P
H
N
N
O
Me
Me
Me
O
O
Me
N
O
Me
3
Cu
O
PTA=O
O
O
Cu(MeCOO)
O
2
MeOH, r.t.
Cu
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
Me
O
Me
O
N
Me
O
O
Cu
Me
O
Me
H
Me
Cu
O
Me
O
O
Me
O
O
O
Me
N
O
O
N
O
Cu
P
O
Cu
O
N
Me
O
O
O
P
Cu
O
O
N
O
O
PTA=O
MeCN, reflux
Me
P
Cu
N
N
O
Cu
O
N
1
O
O
O
N
O
O
N
Me
Me
Cu
O
Me
Me
2
Scheme 1. Synthesis and structural formulae of 1–3.
–
1
The IR spectra of 1–3 exhibit a set of vibrations in the 1450−550 cm range typical for PTA
7
ꢀ19
and PTA=O moieties,
as well as several highly intense bands due to the vas(COO)
−1
−1
36
(
1620−1421 cm ) and v (COO) (1372−1337 cm ) vibrations of acetate ligands. Other
s
–1
37
characteristic vibrations concern the weak v(CH) bands in the 2968−2831 cm range.
ꢀ
1
Additionally, the IR spectrum of 2 shows a characteristic band of the P=O group at 1182 cm ,
which is shifted in comparison to that in an uncoordinated or Nꢁcoordinated PTA=O (1165
ꢀ1
11
ꢀ1
cm ) moiety. The IR spectrum of 1 exhibits a P=O band at 1156 cm due to Hꢀbonding
interaction between the PTA=O and [Cu (µꢀMeCOO) (MeOH) ] units. The distances of P=O
2
4
2
bonds in the crystal structures of 1 and 2 are equal to 1.4985(18) and 1.495(4) Å, respectively.
These distances differ just by 0.004 Å, although from the different coordination modes of the
PTA=O moieties in 1 and 2 (nonꢀcoordinated in 1 and copperꢀcoordinated in 2) as well as
–
1
from the different wavelengths of their ν(P=O) IR bands (1156 and 1182 cm , respectively),
one may expect a larger difference in the P=O bond lengths. However, this observation is in
accord with the statistical distribution obtained from the Cambridge Structure Database (Table
S4), which reveals average P=O bonds lengths of 1.490 and 1.497 Å for PTA=O having nonꢀ
coordinated oxygen and that coordinated to a transition metal, respectively. Moreover, the
P=O bond distances range from ca. 1.47 to 1.51 Å in both cases (Table S4), thus not allowing
to build a clear correlation between the coordination mode of PTA=O and its P=O separation.
Structural and Topological Description
Compound [Cu
2
(µꢁMeCOO)
4
(MeOH)
2
](PTA=O)
2
(1). The crystal structure of 1 is
composed of a discrete 0D [Cu
2
(µꢁMeCOO)
4
(MeOH) ] unit and two uncoordinated PTA=O
2
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moieties (Figure 1). The copper(II) dimer represents a neutral paddleꢀwheel tetraacetate block
wherein each Cu1 center also has a terminal methanol ligand. The Cu1…Cu1 separation of
2.6041(5) Å lies within the typical values observed in other dicopper(II) paddleꢀwheel
38
derivatives. If the Cu1…Cu1 interaction is not taken into consideration, the geometry
around the fiveꢀcoordinate Cu1 centers can be described as a distorted squareꢀpyramid with a
{
CuO
5
} environment, which is filled by four acetate O2–O5 oxygen atoms [avg. Cu–O
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
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
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2
3
4
5
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8
9
0
1
2
3
4
5
6
7
8
9
0
1
.964(7) Å] and the O6 atom from the MeOH ligand [2.1607(18) Å]. Besides, two symmetry
equivalent PTA=O moieties are Hꢀbonded to a dicopper(II) unit.
2
4 2
Figure 1. Structure of 1 showing a dicopper(II) paddleꢀwheel unit [Cu (µꢀMeCOO) (MeOH) ] and its
Hꢀbonding interaction with PTA=O moieties. Further details: H atoms (apart from those participating
in Hꢀbonds) are omitted for clarity, color codes: Cu (green), O (red), N (blue), P (orange), C (gray), H
(
dark gray).
Compound [Cu
structure of 2 is significantly more complex, given the presence of three structurally distinct
copper(II) atoms (Cu1, Cu2, and Cu3) interconnected by the µꢀacetate linkers and the µ
3 6 3 n
(µꢁMeCOO) (ꢀ ꢁPTA=O)] ꢂ3.5nMeCN (2). In contrast to 1, the crystal
3
ꢀ
PTA=O spacers (Figure 2a). The latter act as unusual tridentate N,N,Oꢀligands and sew
adjacent dicopper(II) paddleꢀwheel blocks into an intricate 3D metalꢀorganic framework
(Figure 2b). Within the three different [Cu
equivalent Cu1, Cu2, or Cu3 atoms, the Cu…Cu separations vary from 2.5732(13) to
.5936(14) and 2.6146(14) Å, respectively. The fiveꢀcoordinate copper centers show the
slightly distorted {CuNO } (Cu1 and Cu2) or {CuO } (Cu3) coordination environments. The
2 4
(µꢀMeCOO) ] blocks based on a pair of symmetry
2
4
5
coordination sphere of the Cu1 atom is filled by four acetate O1–O4 atoms [avg. Cu1–O
1.971(4) Å] and an axial N1 atom from the µ ꢀPTA=O block [Cu1–N1 2.221(4) Å]. Similarly,
3
the coordination environment of the Cu3 center is taken by four acetate O9–O12 atoms [avg.
Cu3–O 1.970(4) Å] and an axial O13 atom from the phosphine oxide ligand [Cu3–O13
2.171(4) Å]. Compound 2 represents the first example of a copperꢀcontaining 3D MOF that is
driven by a PTA=O or any other PTAꢀderived block.
(a)
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2
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2
2
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2
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9
0
1
2
3
4
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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
(b)
(c)
Figure 2. Structural fragments of 2: (a) coordination environment around Cu1, Cu2, and Cu3 atoms,
(b) 3D metalꢀorganic framework, and (c) its topological representation showing a decorated uninodal
ꢀconnected underlying net with the ths topology. Further details: (a, b) H atoms are omitted for
clarity, color codes: Cu (green), O (red), N (blue), P (orange), C (gray); (b, c) views along the a axis;
3
(
c) Cu atoms (green), centroids of PTA=O nodes (cyan), centroids of acetate moieties (gray).
To better understand the framework structure of 2, we have performed its topological
3
9ꢀ42
analysis by applying the concept of the simplified underlying net.
Such a net has been
generated by reducing the µꢀMeCOO and ꢀ
maintaining their connectivity. From the topological viewpoint, the resulting underlying
framework (Figure 2c) can be considered as a combination of the 2ꢀconnected [Cu (µꢀ
MeCOO) ] secondary building units (SBUs) and 3ꢀconnected ꢀ ꢀPTA=O nodes. Hence, the
topological analysis reveals a decorated uninodal 3ꢀconnected net with the ths (ThSi
3
ꢀPTA=O ligands to respective centroids and
2
4
3
2
)
3
9ꢀ42
3
topology
and point symbol of (10 ).
(a)
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8
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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
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5
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5
5
5
6
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
(
b)
c)
(
Figure 3. Structural fragments of 3: (a) coordination environment around Cu1 and Cu2 atoms, (b) 1D
waveꢀlike metalꢀorganic chain, and (c) its topological representation showing a uninodal 2ꢀconnected
underlying net with the 2C1 topology. Further details: (a, b) H atoms are omitted for clarity, color
codes: Cu (green), O (red), N (blue), P (orange), C (gray); (b, c) views along the c axis; (c) Cu atoms
(
green), centroids of PTA (cyan) and acetate (gray) moieties.
3 4 2 n
Compound [Cu (µꢁMeCOO) (MeCOO)(µꢁPTA) (PTA)] (3). This structure represents
a rare example of a mixedꢀvalence Cu(II)/Cu(I) 1D coordination polymer driven by the µꢀ
PTA linkers. It bears three Cu atoms (two divalent Cu1 and one monovalent Cu2), four µꢀ
bridging and one terminal acetate ligands, as well as two µꢀbridging N,Pꢀbound and one
terminal Pꢀbound PTA ligands, per formula unit (Figure 3a,b). As in the case of 1 and 2, the
copper(II) atoms in 3 are arranged into paddleꢀwheel dimeric units with the Cu1…Cu1
separation of 2.5951(10) Å. Each Cu1 atom can be considered as fiveꢀcoordinate with a
4
distorted squareꢀpyramidal {CuNO } environment, filled by four acetate O1–O4 atoms [avg.
Cu1–O 1.968(3) Å] in equatorial sites and a nitrogen atom from the µꢀPTA moiety [Cu1–N4
2.225(3) Å] in the axial site. The fourꢀcoordinate Cu2 atoms reveal a distorted tetrahedral
{
3
CuP O} environment, which is taken by a pair of symmetry generated P2 atoms [Cu2–P2
2.2739(12) Å] from the µꢀPTA spacers and the P1 and O5 atoms from the terminal PTA and
acetate ligands [Cu2–P1 2.2664(17), Cu2–O5 2.024(5) Å], respectively. The monocopper(I)
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6
[
Cu(PTA)(MeCOO)] and dicopper(II) [Cu (µꢀMeCOO) ] blocks are interconnected by the µꢀ
2 4
PTA spacers to generate an infinite 1D waveꢀlike chain (Figure 3b). From the topological
3
9,40
perspective,
this chain can be considered as a uninodal 2ꢀconnected underlying net (Figure
3
c) with a decorated 2C1 topology. An unusual feature of this structure concerns the presence
of monovalent and divalent copper centers, as well as two different N,Pꢀ and Pꢀbound PTA
ligands.
0
1
2
3
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1
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0
1
2
3
4
5
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7
8
9
0
Magnetic Studies. The magnetic properties of 1–3 were investigated over the
temperature range of 1.8–300 K. Plots of magnetic susceptibility χ
is the molar magnetic susceptibility for two Cu(II) ions) are given in Figures S4 (SI) and 4,
respectively. For 1–3, the χ T values at 300 K are much below those expected for two
magnetically isolated spin doublets [ χmT = 2(N
m m m
and χ T product vs. T (χ
m
2
2
3
–1
β
g /3k)S(S +1) = 0.749 cm mol K, wherein g
=
2.1 is the spectroscopic splitting factor, N – the Avogadro’s number, β – the Bohr
43
magneton, k – the Boltzmann’s constant, and S = ½], being equal to 0.538, 0.584, and 0.621
3
–1
m
cm mol K, respectively (Figure 4). The χ T plots continuously decrease on lowering the
temperature reaching almost zero below 50 K. These features are indicative of a strong
antiferromagnetic coupling between the copper(II) ions in these compounds, for which the
diamagnetic ground state is completely populated below 50 K. Additionally, the susceptibility
curves for 1–3 exhibit the maximum that confirms the presence of a strong antiferromagnetic
N
ordering with a Neel temperature (T ) about 300 K (Figure S4).
The variation of the magnetization (M) with respect to the field (H), at 2 K, also
confirms the nature of the ground state in 1–3. The results are depicted in Figure 5, where the
molar magnetization M (per Cu
attain the saturation in the applied field range and the magnetization values at 5 T are much
below 1 µ . The magnetization curves for 1–3 are reproduced by the equation
M = g SNB (x)
2 B
entities) is expressed in µ units. The compounds 1–3 do not
B
43
(S = 2S ), where B (x) is the Brillouin function and x = gβH/kT. The
β
Cu
s
s
experimental values are much inferior than those calculated using the Brillouin function for
two nonꢀinteracting copper(II) ions. This further indicates that 1–3 behave as
antiferromagnets.
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.7
.6
.5
0.4
0
.3
.2
1
1
1
1
1
1
1
1
1
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2
2
2
2
2
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2
3
4
5
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8
9
0
χ
0
1
2
3
0.1
.0
0
0
50
100
150
200
250
300
T (K)
II
Figure 4. Temperature dependence of experimental
are the calculated curves derived from equation (1).
χ
m
T (
χ
m
per 2Cu atoms) for 1–3. The solid lines
Although all compounds display distinct metalꢀorganic architectures, they bear similar
dicopper(II) paddleꢀwheel tetraacetate [Cu (µꢀMeCOO) ] blocks. The shortest CuꢁꢁꢁCu
distances between the adjacent dicopper(II) units in 1–3 (8.5069(6), 5.9956(11), and
.4411(6) Å, respectively) are large enough to consider the dinuclear core as magnetically
isolated. Hence, the magnetic data of 1–3 were analysed using the isotropic spin Hamiltonian
2
4
6
r
r
H = −JS ⋅ S that results in the BleaneyꢀBowers expression for two interacting spin doublets,
1
2
4
3,44
eq (1).
The paramagnetic monomeric impurity
ρ
was introduced in eq (1) to obtain
44
satisfactory results.
2
2
2
2
2
Nβ
g
Nβ g
χm
=
(1−
ρ
) +
ρ
kT[3 + exp(−J / kT)
2kT
(1)
stands for the molar fraction
of the monomeric form, while the other parameters have their usual meaning. A leastꢀsquares
In equation (1), J is an intradimer exchange coupling constant,
ρ
−1
fitting of the experimental data leads to the following values: J = –320(1) cm , g = 2.20(1),
−
4
−1
ρ
= 0.024, and R = 3.75·10 for 1, J = –310(2) cm , g = 2.24(1), ρ = 0.016, and R =
−4
−1
−4
2
.91·10 for 2, and J = –320(1) cm , g = 2.25(2),
ρ
= 0.022, and R = 1.08·10 for 3. The
calculated curves very well reproduce the magnetic data in the whole temperature range
(
Figure 4). The criterion applied to determine the best fit was based on the minimization of
2
2
the sum of squares of the deviation, R = Σ(χexpT – χcalcT) /Σ(χexpT) . Results of the magnetic
data calculations for 1–3 indicate a strong antiferromagnetic coupling between the copper(II)
ions transmitted through µꢀacetate linkers.
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The magnetoꢀstructural relationship in the carboxylatoꢀbridged copper(II) compounds
shows that the nature and the strength of magnetic exchange coupling can depend on the type
of bridging mode, the coordination geometry of copper(II) centers, the CuꢁꢁꢁCu distances, and
4
5ꢀ59
mainly on the bond angles at bridging atoms and the number of bridges.
Typically, an
exchange coupling constant significantly declines when the number of carboxylate bridges
58
59
decreases from 4 to 1. Furthermore, Wieghardt proposed a relationship between J/n and
the Cu–O–C bond angle ( ) in which n is the number of carboxylate bridges. Larger angles
thus lead to smaller coupling values. The results obtained for 1–3 are consistent with a more
general observation that the tetraꢀ ꢀcarboxylateꢀbridging species strongly mediate an
exchange coupling. The mechanism of the antiferromagnetic coupling between the copper(II)
0
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2
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α
α
ꢀ
2
2
y
ions in 1–3 is an effect of the interaction of the d − orbitals positioned in the square base
x
via the acetate oxygen atoms.
2
1
.0
.5
1
2
3
0.015
0.010
0.005
ꢀ
1.0
ꢀ
0
0
.5
.0
1
2
3
0
.000
0
1
2
3
4
5
H (T)
0
1
2
3
4
5
H (T)
Figure 5. Field dependence of the magnetization (M per Cu
Brillouin function curve for the system of two uncoupled spins with S = /
2
entities) for 1–3. The solid line is the
1
2
and g = 2.0.
EPR Spectra. The EPR spectra of solid samples 1–3 at 298 and 77 K additionally
confirm the properties determined by direct magnetic measurements (Figure S5). The
polycrystalline Xꢀband EPR spectra of compounds 1–3 show no significant difference
between room temperature and 77 K. Compared with the spectrum at 77 K, the signals at 298
K are much sharper and stronger. The EPR spectra of 1–3 are typical for compounds where an
2
2
60ꢀ65
unpaired electron is in a dx −y ground state.
The EPR spectra are also typical for dimeric
60ꢀ63,66,67
copper(II) species with an Oꢀenvironment.
The spectra exhibit transitions in low and
high field regions (380 G and 4700 G). The observed hyperfine pattern in low field region
proves the presence of intradimer magnetic exchange interactions as detected by the direct
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magnetic measurements. The spectra also display a line at 3200 G that can be attributed to a
monomeric impurity (g = 2.08 for 1, g = 2.06 for 2, and g = 2.07 for 3).
Catecholase Activity Studies. Good solubility of 1 and 2 in nonꢀaqueous solvents
encouraged us to investigate their catalytic activity under homogeneous conditions in the
aerobic oxidation of 3,5ꢀdiꢀtertꢀbutylꢀcatechol (3,5ꢀDTBC) to the corresponding diketone,
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
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8
9
0
68ꢀ72
3
,5ꢀdiꢀtertꢀbutylꢀoꢀbenzoquinone (3,5ꢀDTBQ) as a model reaction (Scheme 2).
Product
o
formation was monitored by UVꢀVis spectroscopy in MeOH at 25 C in air. Control
experiments carried out under similar reaction conditions but in the absence of copper catalyst
confirmed no conversion of 3,5ꢀDTBC to 3,5ꢀDTBQ. Upon addition of the 3,5ꢀDTBC
substrate to a MeOH solution of catalyst 2, an increase in the absorption band of the 3,5ꢀ
DTBQ product is observed (Figure 6). Similar dependences for catalyst 1 and copper(II)
acetate (control experiment) and a mixture composed of copper(II) acetate with PTA=O are
given in Supporting Information (Figures S7–S9). Maximum initial reaction rate (Vmax) and
MichaelisꢀMenten constant (K ) were determined from the MichaelisꢀMenten plots (Figures
M
7 and S10 for 2, S11, S12 and S13 for 1, for copper acetate, and a mixture of copper acetate
and PTA=O, respectively). The obtained values of maximum initial reaction rates for 1 and 2
ꢀ3
ꢀ3
ꢀ1
are 3.24×10 and 5.26×10 M·min , respectively (Table 1). The catalyst turnover frequencies
ꢀ1
(kcat) were measured as a ratio of Vmax/[catalyst] and attain values of 49.62 and 80.92 min for
and 2, respectively. Resembling kinetic parameters were observed for 1 and a catalyst
1
formed in situ from copper(II) acetate and PTA=O in 1:1 molar ratio, showing similar nature
of active species. It is important to highlight that these turnover frequencies are twoꢀ or fourꢀ
ꢀ1
fold superior than the value of 20.88 min determined herein for copper(II) acetate as well as
7
0ꢀ72
in comparison with other catalysts.
Hence, compounds 1 and 2 can be considered as very
promising bioinspired catalysts for the oxidation of catechols.
t
t
Bu
Bu
catalyst
air
t
t
HO
Bu
O
Bu
OH
O
Scheme 2. Schematic representation of the oxidation of 3,5ꢀDTBC to 3,5ꢀDTBQ.
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0
Figure 6. Time sequences showing an increase in the absorption band at 390 nm of 3,5ꢀDTBQ in the
oxidation of 3,5ꢀDTBC (1.33×10 M, 2.0 mL MeOH) catalyzed by 2 (6.50×10 M, 1.0 mL MeOH);
ꢀ
2
ꢀ5
°
2
5 C, in air.
Figure 7. Catecholase activity of 2: MichaelisꢀMenten plot.
Table 1. Kinetic parameters for the aerobic oxidation of 3,5ꢀDTBC to 3,5ꢀDTBQ catalyzed by 1, 2,
Cu(MeCOO)
Catalyst
2 2
and Cu(MeCOO) + PTA=O (molar ratio 1:1) in MeOH.
a
ꢀ1
a
2 a
ꢀ1
V
max [M min ]
K
M
[M]
R
k
cat [min ]
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*
ꢀ3
ꢀ5
ꢀ4
ꢀ4
ꢀ3
Cu(MeCOO)2
1.42×10
8.24×10
1.14×10
1.28×10
1.83×10
0.91179
0.88345
0.93948
0.97177
20.88
42.22
49.62
80.92
ꢀ3
Cu(MeCOO)
2
+PTA=O 2.63×10
ꢀ3
1
2
3.24×10
ꢀ3
5.26×10
a
*
Value for MichaelisꢀMenten plot, calculated for monomeric copper(II) acetate.
1
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0
Conclusions
In the present work, we further explored a still very limited usage of aquaꢀsoluble
cageꢀlike aminophosphine PTA and its Pꢀoxide derivative toward the selfꢀassembly
generation of unusual coordination polymers. In fact, a slight variation of reaction conditions
and modification of principal building block (PTA=O vs. PTA) resulted in the assembly of
three distinct products 1–3, which all bear dicopper(II) paddleꢀwheel tetraacetate units.
However, the compounds 1–3 reveal different dimensionality and structural and topological
features, as well as magnetic properties. Topological analysis has disclosed a decorated
uninodal 3ꢀconnected framework with the ths topology in 2 and a uninodal 2ꢀconnected chain
with the decorated 2C1 topology in 3.
Despite revealing different structural features, compounds 1–3 show similar magnetic
and EPR spectroscopic properties owing to the presence of dicopper(II) paddleꢀwheel
tetraacetate [Cu
2
(µꢀMeCOO
)
4
] blocks. Magnetic properties were investigated and modelled,
blocks
disclosing a strong antiferromagnetic coupling between copper atoms within the Cu
2
that can be rationalized by the BleaneyꢀBowers expression. The nature and magnitude of the
magnetic couplings were discussed on the basis of structural parameters.
Furthermore, the obtained compounds 1 and 2 were applied as powerful bioinspired
catalysts for the aerobic oxidation of 3,5ꢀdiꢀtertꢀbutylꢀcatechol to 3,5ꢀdiꢀtertꢀbutylꢀoꢀ
ꢀ1
benzoquinone, resulting in catalyst turnover frequency values of up to 81 min .
The present study also extended a still very limited family of CuꢀPTA=O and CuꢀPTA
coordination polymers to novel and rather unique examples. In fact, compound 2 represents
the first 3D copperꢀbased metalꢀorganic framework that is driven by PTA=O or any other
PTA derivative, whereas compound 3 features an unusual mixedꢀvalence copper(I/II)
coordination polymer wherein PTA blocks act as both linkers and terminal ligands. Further
research aiming at the application of PTA=O, PTA and related cageꢀlike building blocks for
the design of new functional coordination polymers is currently in progress.
Acknowledgments: This work was supported by the NCN program (Grant No.
2012/07/B/ST5/00885), Poland, and by the FCT, Portugal (UID/QUI/00100/2013 and
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SFRH/BPD/99533/2014). We gratefully thank Miłosz Siczek (University of Wrocław) for
collecting Xꢀray diffraction data and Małgorzata Gajewska (Academia Sinica, Taiwan) for
help with catecholase activity studies.
Supporting Information Available: additional figures (Figures S1ꢀS22), tables (Tables S1ꢀ
S4) and crystallographic files in CIF format for 1ꢀ3. This material is available free of charge
via the Internet at http://pubs.acs.org.
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phosphaadamantane Salt ꢀ [mPTA]BF . Inorg. Chem. 2015, 54, 434ꢀ440.
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For Table of Contents Use Only
Unique
Copper-Organic
Networks
Self-Assembled
from
1,3,5-Triaza-7-
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Phosphaadamantane and its Oxide: Synthesis, Structural Features, Magnetic and
Catalytic Properties
Ewelina I. Śliwa, Dmytro S. Nesterov, Julia Kłak, Piotr Jakimowicz, Alexander M. Kirillov,
and Piotr Smoleński
TOC graphic
Synopsis
New types of copperꢀorganic networks were assembled from cageꢀlike aminophosphine
building blocks; their structural features, magnetic and oxidation catalytic properties were
investigated.
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