Coordination Polymers based on the Neutral Ditopic Ligand (C6H4PO(OCH3)2)2 Involving some f-Block Elements

Article abstract of DOI:10.1002/zaac.201700424

An improved synthesis using microwave heating affords (C₆H₄PO(OCH₃)₂)₂ in excellent isolated yield (95 %). The ligand properties of this bisphosphonateester were explored towards hard metal centers M<

Full text of DOI:10.1002/zaac.201700424

Title: Coordination polymers based on the neutral ditopic ligand
C₆H₄PO(OCH₃)₂)₂ involving some f-Block elements
(
Authors: Rudolf Pietschnig, Kristijan Krekic, Eireen Käkel, Dieter
Klintuch, and Dana Bloß
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To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.201700424
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Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201700424
ARTICLE
Coordination polymers based on the neutral ditopic ligand
PO(OCH involving some f-Block elements
(C
6
H
4
3
) )
2 2
[a]
[a]
[a]
[a]
[a]
Kristijan Krekić, Eireen Käkel, Dieter Klintuch, Dana Bloß and Rudolf Pietschnig*
Dedicated to Professor Dietrich Gudat on the Occasion of his 60th Birthday
Abstract: An improved synthesis using microwave heating affords (C
properties of this bisphosphonate have been explored towards hard metal centers M (M = Ca, UO
6 4 3 2 2
H PO(OCH ) ) in excellent isolated yield (95%). The ligand
2
+
) and M3+ (M = La, Ce, Sm, Eu)
2
resulting in coordination polymers for which the reduction of ionic size of the metal center resulted in lower-dimensional structural motifs
as opposed to higher dimensional networks obtained for the larger ions. All coordination polymers were characterized by single crystal
X-ray diffraction, IR spectroscopy and combustion analysis. The ligand was furthermore characterized with multinuclear NMR
spectroscopy.
Introduction
is in a similar region as closely related compounds.[9] Solid L
shows two IR bands characteristic for phosphonates at 1246 and
1178 cm .
-1 [8, 9]
Owing to their unique physical properties, lanthanide nitrate
based coordination polymers have attracted substantial interest
over several decades in addition to their interesting structural
features.[ Therefore such coordination polymers are relevant in
a wide range of technological fields, such as medicine, LEDs,
lanthanide separation, etc..[5] The most frequently used binding
sites in metal-organic frameworks or coordination polymers are
carboxylates or nitrogen bases.[1, 6] In recent times phosphonates
are being explored due to the possibility of accessing new metal
phosphate morphologies.[7] By contrast neutral phosphonate
esters have not been so widely explored as ligands.[3, 8] Very
recently we reported an optimized synthesis of such ditopic
phosphonate esters giving improved yields at reduced reaction
times using microwave heating.[9] This stimulated us to explore
1-4]
Scheme 1. Synthesis of L and coordination polymers 1a-f.
the solvent free microwave
PO(OMe) which has been mentioned in literature before
however with very limited characterization.
assisted synthesis of
(
C
6
H
4
2 2
)
̅
Compound L crystallizes in space group P 1 . Owing to an
inversion center located at the central C-C bond, only half of the
ligand is present in the asymmetric unit resulting in co-planar
arrangements of the phenyl rings (Fig 1.). The P=O bond length
[
10]
So far the ligand
properties have been explored with cadmium[11] and
manganese[ as a metal centers, affording a two dimensional
coordination polymer. Here we further report the use this ligand
for complexation with lanthanides and earth alkaline metals, as
well as uranium.
12]
[
3,
is 1.4619(16) Å and within standard deviation for similar bonds.
9
, 13]
The P—O single bonds are 1.5812(16) and 1.5778(15) Å
respectively. The angles around the phosphorus atom cover a
range of 101.31(9) to 115.73(9)°. They show slight deviation from
tetrahedral angles due to interactions with neighboring molecules.
Results and Discussion
Starting from 4,4’-dichloromethylbiphenyl and trimethyl phosphite
we have been able to prepare compound L on a multigram scale
in excellent yield using microwave heating (Scheme 1). The 31P
NMR spectrum in solution shows a signal at 28.9 ppm split to a
multiplet owing to phosphorus proton coupling (2JPH=22 Hz) and
[
a]
K. Krekić, Prof. Dr. R. Pietschnig
Institute of Chemistry and CINSaT, University of Kassel
Heinrich-Plett-Straße 40, 34132 Kassel (Germany)
E-mail: pietschnig@uni-kassel.de
Fig 1. Solid state structure of ligand L. Ellipsoids are drawn at 30 % probability
level.
The formation of coordination polymers can be achieved by slow
evaporation of a methanol solution of L and a corresponding
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
Ln(NO
3 3
) salt. Only in case of lanthanum, cerium, samarium and
europium it was possible to obtain single crystals of good quality
1
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Zeitschrift für anorganische und allgemeine Chemie
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ARTICLE
for x-ray analysis. Two new types of structures were found. In
addition, all compounds were also characterized by elemental
analysis and IR spectroscopy. The coordination polymers 1a and
Going down the line to samarium 1c and europium 1d, again
isostructural coordination polymers have been found albeit with
different binding motif compared to coordination polymers 1a,b.
Only the structure of the samarium compound 1c will be described
which is also representative for 1d. The polymer crystallizes in
1
b show two almost identical vibrational bands at 1206 and 1172
-1
cm and are shifted towards lower wavenumbers compared to the
̅
space group P1. Formally the asymmetric unit is built of one
uncoordinated ligand L. The bands for 1c and 1d are also almost
identical at 1201 and 1164 cm-1 yet slightly shifted compared to
Sm(NO
3
)
3
center and one and a half ligand. Consequently the
] which is further
repeating unit of the polymer is [[Sm(NO ) ] L
3 3 2 3
1
a, 1b. The large shift of P–O vibrational band in both free ligand
corroborated by elemental analysis. The metal is coordinated to
three bidentate nitrate units and three monodentate ligands rising
up to a coordination number of 9 (Fig 4).
-1
(
1178 cm ) and complexes compared with the previously
i
-1
6 4 2 2
published ligand ((C H PO(OPr) ) (1105 cm ) is due to the
different steric situation as a consequence of the reduced size of
the substituents at the oxygen atoms in 1a-d.
The coordination polymers of lanthanum 1a and cerium 1b
are isostructural. Therefore only the cerium structure will be
described which is representative for both. The polymers
crystallizes in a P2
of one Ce(NO unit and two symmetry independent ligands L.
The repetition unit of the polymer backbone is [Ce(NO ] which
1
space group and the asymmetric unit consists
3 3
)
3 3 2
) L
is further confirmed by elemental analysis. The coordination
sphere around the central metal atom consists of three bidentate
nitrate anions and four monodentate phosphonate units as part of
ligand L, adding up to a coordination number of 10 (Fig 2.).
Figure 4. Coordination sphere of 1c. Ellipsoids are drawn at 30% probability
level.
The bond lengths between the samarium and nitrate oxygen
atoms are in the range of 2.487(3) to 2.531(4) Å and slightly
smaller than those found for the cerium derivate which is in
accordance with the smaller ionic radius of samarium compared
with cerium. The bonds between samarium and the phosphonate
ester oxygen atom are as well slightly shorter covering the range
from 2.325(3) to 2.380(3) Å. Two ligands bridge two metal centers,
thus forming a dimer. Those dimers are bridged by a third ligand
forming a 1D chain (Fig 5). The biphenyl units within the dimers
show a disorder in half of the phenyl units leading to dihedral
angles of 33.6(3) and 44.4(3)° between the phenyl units. By
contrast, in the bridging ligand the biphenyl unit is planar. The
distance between the metal centers of the dimeric part is 15.488
Å, while that between two dimers amounts to 18.791 Å. The
general topology of 1c and 1d is related to other 1D-polymeric
structures based on d-block metals with macrocyclic
Figure 2. Coordination sphere of 1b. Ellipsoids are drawn at 30 % probability
level.
The bond lengths from cerium to the nitrate oxygen atoms are in
the range of 2.565(10) to 2.675(8) Å and do not deviate from
similar coordination polymers. On the other hand the bond lengths
of cerium to oxygen atoms belonging to phosphonate ester
groups are shorter and in the range of 2.413(11) to 2.489(9) Å.
The polymer forms a rhombic pattern within one sheet. The angle
between vertices of the rhomb is 100.61° with distances between
neighboring cerium atoms being 18.157 Å. The dihedral angles of
biphenyl units are 32.1(4) and 24.2(4)° respectably. The two
neighboring sheets are interpenetrated (Fig 3.).
[14, 15]
arrangements containing lateral -systems.
Figure 5. Ball and stick model of 1c showing the polymeric motif. Hydrogen
atoms are emitted for clarity.
For the sake of comparison the calcium analog 1e has been
investigated as well. The calcium coordination polymer
̅
crystallizes in space group I42d. In the asymmetric unit the
calcium atom is found on a fourfold axis with half of a nitrate and
ligand. Due to the high symmetry the repeating unit of the
coordination polymer is [Ca(NO ) L ]. The coordination
3 2 2
environment of one calcium ion consists of two bidentate nitrate
and four phosphonate ligands, which adds up to a total
coordination number of 8. The bond length between the calcium
and oxygen atoms of nitrate is 2.572(8) Å and thus in a similar
range as in 1b. As expected the contact between the calcium ion
and the oxygen atom of the phosphonate ester unit is shorter than
in the previously discussed coordination polymers, 2.331(11) Å.
The structural motif consists of a square pattern within one sheet,
with distances between neighboring calcium atoms of 18.237 Å.
The next sheet is intertwined with the first one forming a mesh
network (Fig 6).
Figure 3. Solid state packing of 1b showing interpenetrated sheets.
2
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Zeitschrift für anorganische und allgemeine Chemie
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ARTICLE
material. The emission spectra obtained from ligand centered
excitation at 332 nm can be assigned to all seven literature known
europium emissions suggesting an antenna like effect energy
transfer from ligand to metal, with quantum yield of 32% (Fig. 10).
The photophysical properties of the europium coordination
polymer revealed
a similar antenna effect as in related
[
9]
coordination polymers albeit with lower quantum yield. The
uranium coordination polymer 1f shows characteristic uranium-
centered emissions (spectra provided in supporting information).
Ligand-centered excitation at 283 nm results in both uranyl- and
ligand-centered emission suggesting a very poor antenna effect
in this case. On the other hand metal-centered excitation at 415
nm results exclusively in uranyl-centered emission and no
radiative energy transfer to the ligand is observed. Independant
of the excitation wavelength (415 nm or others), the uranium-
centered emissions show very low quantum yields (<1 %)
suggesting higher vibrational relaxation in case of phosphonate
Figure 6. Packing of 1e showing interpenetrated mesh network.
Using uranium as coordination center, starting from uranyl nitrate,
the respective coordination polymer 1f gives a one-dimensional
zig-zag type polymer backbone (Fig 7). In the solid state 1f
[16, 17]
ester coordination.
̅
crystallizes in space group P1, where in the asymmetric unit the
uranium atom is located on an inversion center. This corresponds
formally to an occupation of half an uranyl unit with one bidentate
nitrate ligand and in addition one half of ligand L. Therefore, the
repeating unit of coordination polymer 1f can be described as
[
2 3 2
UO (NO ) L] which is further corroborated by the composition
based on elemental analysis. The coordination number of
uranium atom is 8 for which a hexagonal bipyramidal geometry is
observed (Fig 8.).
Figure 9. Normalized excitation and emission of solid ligand L.
Figure 7. Ball and stick model of the zig-zag chain in 1f.
Figure 10. Normalized excitation and emission of solid 1d.
Figure 8. Coordination sphere of 1f showing hexagonal bipyramidal
coordination of the central uranium atom. Ellipsoids are draw at 30% probability
level.
Conclusions
The bond length of uranium to oxygen atoms of nitrate unit are
To conclude, we have explored the ligand properties of
(C H PO(OMe) ) towards selected lanthanides, calcium and
6 4 2 2
2.525(4) and 2.509(4) Å respectfully. The bond length between
the uranium and the phosphonate-based oxygen atom is 2.365(3)
Å which, in agreement with other examples, is shorter than the
corresponding contact to the nitrate. The distance between two
uranium atoms in the polymer backbone is 14.152 Å which is
considerably shorter than the intermetallic distances of polymers
uranium for the first time. In case of the lanthanide coordination
polymers the reduction of ionic size of the metal center resulted
in lower-dimensional structural motifs of the polymer. In case of
lanthanum and cerium a two dimensional interpenetrated sheet
polymer was obtained. On the other hand samarium and
europium form a one dimensional polymer with macrocyclic units
containing laterally assembled -systems within the polymeric
chain. Calcium and uranium showed similar affinity for
phosphonate ester coordination as the lanthanides mentioned
before forming 1D-coordination polymers as well. In the future we
would like to take advantage of the structural variety of
phosphonates to further explore the ligand behavior towards f-
block metals in analogy to the rich coordination chemistry of the
isolobal silanetriols.[
1a-e. Given the unique luminescence behavior of some of the
elements involved, we explored the photophysical properties of
ligand L and the europium and uranyl coordination polymers 1d,
f in the solid state. The ligand itself shows an emission quantum
yield of 29 % at the excitation wavelength of 366 nm with an
emission maximum at 417 nm (Fig. 9). The excitation spectrum of
polymer 1d shows a hypsochromic shift of the ligand based
excitation to 332 nm. The europium based excitation remains
3 3
unchanged compared to Eu(NO ) that was used as a starting
18-21]
3
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ARTICLE
Table 1. Crystallographic data and structure refinement for L and 1a-f.
L
1a
1b
1c
1d
1e
1f
Empirical formula
Formula weight
Crystal description
Crystal size [mm]
Crystal system, space group
Radiation and λ [A]
Monochromator
Temperature [K]
Unit cell dimensions:
a [Å]
b [Å]
c [Å]
α [°]
β [°]
γ [°]
Volume [ų]
Z
C
18
H
24
O
6
P
2
C
36
H
48LaN
3
O
21
P
4
C
36
H
48CeN
3
O
21
P
4
C
27
H
36
N
3
O
18
P
3
Sm
C
27
H
36EuN
935.46
colorless plate
3
O
18
P
3
C
36
H
48CaN
2
O
18
P
4
18 24 2 14 2
C H N O P U
792.36
colorless block
398.31
1121.56
colorless plate
0.160 X 0.060 X 0.020
monoclinic P 2
1122.77
colorless block
0.230 X 0.127 X 0.070
monoclinic P 2
933.85
colorless plate
960.72
colorless block
colorless plate
0.220 X 0.160 X 0.040
0.140 X 0.060 X 0.020
0.110 X 0.060 X 0.010
0.250 X 0.200 X 0.200
0.160 X 0.120 X 0.060
triclinic P 1̅
triclinic P 1̅
triclinic P 1̅
tetragonal I 4̅ 2d
triclinic P 1̅
1
1
Mo K\α 0.71073
Graded multilayer mirror
100(2)
Mo K\α 0.71074
plane graphite
100(2)
Mo K\α 0.71075
plane graphite
100(2)
Mo K\α 0.71076
plane graphite
100(2)
Mo K\α 0.71077
plane graphite
100(2)
Mo K\α 0.71078
plane graphite
100(2)
Mo K\α 0.71079
plane graphite
100(2)
6.6655(6)
8.1466(6)
9.4308(8)
74.575(6)
74.846(7)
74.344(6)
465.32(7)
1
9.5823(9)
23.451(2)
9.9136(9)
90
91.913(7)
90
9.6779(7)
23.5561(9)
10.0275(6)
90
92.229(6)
90
8.7345(5)
10.0870(6)
21.8040(14)
89.380(5)
89.143(5)
66.245(4)
1758.06(19)
2
8.6833(7)
21.923(2)
10.0974(9)
89.783(8)
114.055(6)
90.593(7)
1755.2(3)
2
12.8952(5)
12.8952(5)
25.7346(11)
90
6.6921(6)
8.3224(8)
11.9449(10)
81.331(7)
85.401(7)
85.992(8)
654.42(10)
1
90
90
2226.5(4)
2
2284.3(2)
2
4279.3(4)
4
Calculated density
F(000)
Linear absorption coefficient µ [mm ]
Absorption correction
Unit cell determination
Diffractometer
Radiation source
Scan type
Θ range for data collection
Index ranges
1.421
210
0.266
1.673
1140
1.188
1.632
1142
1.219
1.764
940
1.889
1.770
942
2.006
1.491
2008
0.374
2.011
380
6.393
-
1
integration
STOE X-area
StadiVari
Mo Genix
Omega scan
2.29 - 31.67
-9 <h< 9
11 <k< 11
13 <l< 13
6402 / 2617
2056
0.0370 , 0.0470
0.839
integration
STOE X-area
STOE IPDS 2
Genix Mo HF'
Omega scan
1.74 - 26.44
-11 <h< 11
-28 <k< 28
-12 <l< 12
15655 / 8357
7103
0.0941 , 0.0703
0.968
SHELXL-2014/7
8357 / 516 / 1
1.097
integration
STOE X-area
STOE IPDS 2
Genix Mo HF
Omega scan
1.73 - 26.28
-11 <h< 11
-28 <k< 28
-12 <l< 12
16684 / 8577
7095
0.0477 , 0.0505
0.995
SHELXL-2014/7
8577 / 516 / 1
1.060
integration
STOE X-area
STOE IPDS 2
Genix Mo HF
Omega scan
1.87 - 26.25
-10 <h< 10
-10 <k< 12
-26 <l< 26
13146 / 6603
5530
0.0339 , 0.0409
0.990
SHELXL-2014/7
6603 / 533 / 0
1.064
integration
STOE X-area
STOE IPDS 2
Genix Mo HF
Omega scan
1.86 - 25.14
-10 <h< 10
-26 <k< 26
-12 <l< 12
13153 / 6614
3844
0.1150 , 0.1390
0.984
SHELXL-2014/7
6614 / 494 / 0
1.024
integration
STOE X-area
STOE IPDS 2
Genix Mo HF
Omega scan
1.59 - 26.19
-14 <h< 4
-15 <k< 15
-31 <l< 27
5414 / 1934
1782
0.0495 , 0.0339
0.996
SHELXL-2014/7
1934 / 111 / 0
1.078
integration
STOE X-area
STOE IPDS 2
Genix Mo HF
Omega scan
1.73 - 26.28
-6 <h< 8
-10 <k< 10
-14 <l< 14
4705 / 2448
2430
0.0307 , 0.0277
0.992
SHELXL-2014/7
2448 / 171 / 0
1.145
-
-
Refl. collected / unique
Significant unique refl.
R(int), R(sigma)
Completeness to Θ = 26.0°
Refinement method
SHELXL-2014/7
2617 / 120 / 0
1.092
Data/parameters/restraints
Goodness-of-fit on F
2
Final R indices [I > 2σ(I)]
R indices (all data)
0.0453
0.0633
0.0962
0.1138
0.0610
0.0744
0.0369
0.0480
0.0878
0.1470
0.1111
0.1160
0.0259
0.0267
Largest difference peak/hole [e/ų]
0.763 / -0.330
2.581 / -2.899
1.590 / -1.188
1.512 / -1.495
1.369 / -2.378
1.282 / -0.827
0.922 / -1.253
4
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Zeitschrift für anorganische und allgemeine Chemie
10.1002/zaac.201700424
ARTICLE
Elemental analysis calc (%) : C 34.73, H 3.89, N 4.50; found: C 34.693 H
3.945 N 4.864
Analysis of 1d
IR(ATR): 1164cm- (m, P-O), 1201cm-1 (st, P=O).
1
Experimental Section
Elemental analysis calc (%): C 34.67, H 3.88, N 4.49; found: C 35.360 H
3
.903 N 4.561
All chemical were purchased from Sigma-Aldrich or TCI and used without
further purification. NMR measurements were done on Varian 400 MHz
and 500 MHz spectrometers. Infrared (IR) spectra were recorded using a
Bruker ATR IR spectrometer with diamond probe. The microwave assisted
synthesis was performed in a CEM DISCOVER-SP reactor in pyrex
vessels closed with Activent-lids. Excitation und emission spectra as well
as luminescent quantum yields (absolute method) measurements were
carried out using a Hamamatsu C11347 system. For the refinement of the
data ORIGIN 2017 was used. Combustion analyses were performed at the
Institut für Chemie, Universität Kassel on a HEKAtech Euro EA elemental
analyzer. Samples were prepared in a Sn cup and analyzed with added
Acknowledgements
The authors would like to acknowledge Dr. Clemens Bruhn and Astrid Pilz
for X-ray measurements, Dr. Martin Maurer for NMR measurements and
the Isotope lab at University of Kassel for use of their facilities. We would
also like to thank the EU ITN SHINE for financial support and the EU-
COST network CM1302 ‘‘Smart Inorganic Polymers’’ (SIPs).
2 5
V O to ensure complete combustion. X-ray diffraction was performed
using either STOE IPDS 2 with image plate (diameter 34 cm) using Mo-
GENIX source (λ=0.71073 nm) or STOE StadiVari with DECTRIS
PILATUS 200K using Mo-GENIX source (λ=0.71073 nm). Structures were
Keywords: phosphorus • uranium • lanthanides • calcium •
coordination modes
[
22]
2
solved using dual space method (SHELXT ) and are refined against F
with SHELXL-2014[23]. All non-hydrogen atoms are refined anisotropically.
Hydrogen atoms were placed on adjacent atoms using a riding model.
[
[2]
1]
S. L. James, Chem. Soc. Rev. 2003, 32, 276.
S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. (Int Ed) 2004,
43, 2334-2375.
[
24]
Further programs used in structure analysis consists of WinGX
,
[
25]
[26]
Mercury
refinement for L, 1a-f are summarized in Table 1. CCDC-1587319-
587325 contain the supplementary crystallographic data for this paper.
and Platon . Details of the structure determinations and
[
[
[
[
3]
4]
5]
6]
J.-W. Zhang, C.-C. Zhao, Y.-P. Zhao, H.-Q. Xu, Z.-Y. Du, H.-L.
Jiang, Cryst. Eng. Comm. 2014, 16, 6635.
O. Guillou, C. Daiguebonne, G. Calvez, K. Bernot, Acc. Chem.
Res. 2016, 49, 844-856.
1
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
M. Murugesu, E. J. Schelter, Inorg. Chem. 2016, 55, 9951-
Synthesis of 4,4' bis(dimethylphosphorylmethyl)biphenyl (L). In
a
9953.
microwave flask 1.5 g (6 mmol) of 4,4’- di(chloromethyl)biphenyl was
placed together with 10 mL (84 mmol) of trimethyl phosphite. The reaction
mixture was heated in a microwave reactor at 160 °C (200 W) under
autogenous pressure for 0.5 hours. After cooling to room temperature flask
was left open for 5 min and was placed back in microwave reactor for 1
hour under same conditions. The resulting solution was concentrated
under reduced pressure which resulted in precipitation of a white solid. The
resulting solid was filtered and washed with cold n-pentane and dried
under reduced pressure. The product was recrystallized from acetone
C. Daiguebonne, N. Kerbellec, O. Guillou, J.-C. Bünzli, F.
Gumy, L. Catala, T. Mallah, N. Audebrand, Y. Gérault, K.
Bernot, G. Calvez, Inorg.Chem. 2008, 47, 3700-3708.
S. K. Gupta, S. K. Langley, K. Sharma, K. S. Murray, R.
Murugavel, Inorg. Chem. 2017, 56, 3946-3960.
L. Zhang, W. Dou, W. Liu, C. Xu, H. Jiang, C. Chen, L. Guo, X.
Tang, W. Liu, Inorg. Chem. Comm. 2015, 59, 53-56.
K. Krekic, D. Klintuch, R. Pietschnig, Chem. Commun. 2017,
[
[
[
[
[
7]
8]
9]
53, 11076-11079.
giving 2.3
g of crystalline product affording 95% yield based on
10]
11]
P. C. Guo, Xitao; Tang, Xuan; Wu, Sufang; Zhang, Jinfeng,
Yingyong Huagong 2010, 35, 2.
X.-D. Zhang, C.-H. Ge, X.-Y. Zhang, C.-Y. Shi, C. He, J. Yin,
Inorg.Chem. Comm. 2008, 11, 1224-1226.
bis(chloromethyl)biphenyl.
1
3
H NMR (400 MHz, CD OD) δ 7.54 (d, J = 8.0 Hz, 4H), 7.35 (m, 4H), 3.68
(
d, J = 10.9 Hz, 12H), 3.27 (d, J = 21.8 Hz, 4H).
31
3
P NMR [1H] (202 MHz, CD OD) δ: 28.9 (m br) ppm.
+
[12]
X. Zhang, C. Ge, J. Yin, Y. Zhao, C. He, Chinese Journal of
Chemistry 2009, 27, 1195-1198.
APCI-MS: m/z=399.07 [M+H]
IR(ATR): 1178 cm (m, P-O), 1246 cm-1 (st, P=O).
-1
[
[
[
[
[
[
[
13]
14]
15]
16]
17]
18]
19]
N. Stock, N. Guillou, J. Senker, G. Férey, T. Bein, Z. Anorg.
Allg. Chem. 2005, 631, 575-581.
B. Nohra, S. Graule, C. Lescop, R. Réau, J. Am. Chem. Soc.
Synthesis of lanthanide(III) coordination polymers: The ligand (100 mg,
0.25 mmol) was dissolved in 5 mL of MeOH. To this solution of the ligand
a solution of Ln(NO xH O(0.25 mmol) in the same solvent was added
3
)
3
2
2
006, 128, 3520-3521.
B. Nohra, Y. Yao, C. Lescop, R. Réau, Angew. Chem. (Int. Ed.)
007, 46, 8242-8245.
Z. Hnatejko, S. Lis, Z. Stryła, J. Therm. Anal. Calorim. 2010,
00, 253-260.
dropwise under heavy stirring at 20°C. Slow evaporation of the solvent
yields colorless crystalline material. (Yield: 1a: 40 mg, 29 %; 1b: 80 mg,
2
58 %; 1c: 50 mg, 32%; 1d: 50 mg, 32 %).
Synthesis of calcium coordination polymer:
The ligand (100 mg, 0.25 mmol) was dissolved in 5 mL of MeOH. To this
1
C. Liu, W. Yang, N. Qu, L.-J. Li, Q.-J. Pan, Z.-M. Sun, Inorg.
Chem. 2017, 56, 1669-1678.
V. Lorenz, A. Fischer, W. Bruser, F. T. Edelmann, K. Jacob, T.
Gelbrich, P. G. Jones, Chem. Commun. 1998, 2217-2218.
V. Lorenz, A. Fischer, S. Gießmann, J. W. Gilje, Y. Gun'ko, K.
Jacob, F. T. Edelmann, Coord. Chem. Rev. 2000, 206-207,
solution of the ligand a solution of CaCl
was added under heavy stirring at 20°C.To the mixture 1 mL of HNO
2
(0.25 mmol) in the same solvent
conc
3
was added. Slow evaporation of the solvent yields colorless crystalline
material. (Yield: 2 mg, 2%)
Synthesis of uranyl coordination polymer: The ligand (100 mg, 0.25
mmol) was dissolved in 5 mL of MeOH. To this solution of the ligand a
2 3 2 2
solution of UO (NO ) xH O (0.25 mmol) in the same solvent was added
321-368.
[
20]
S. Spirk, F. Belaj, J. Baumgartner, R. Pietschnig, Z. Anorg. Allg.
Chem. 2009, 635, 1048-1053.
under heavy stirring at 20°C. Slow evaporation of the solvent yields
colorless crystalline material.
[
[
21]
22]
R. Pietschnig, S. Spirk, Coord. Chem. Rev. 2016, 323, 87-106.
G. Sheldrick, Acta. Crystallogr. A. 2015, 71, 3-8.
G. Sheldrick, Acta. Crystallogr. C. 2015, 71, 3-8.
L. J. Farrugia, J. Appl. Crystallogr. 2012, 45, 849-854.
C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P.
Shields, R. Taylor, M. Towler, J. van de Streek, J. Appl.
Crystallogr. 2006, 39, 453-457.
Analysis of 1a
IR(ATR): 1172 cm (m, P-O), 1206 cm-1 (st, P=O).
-
1
[23]
[
[
24]
25]
Elemental analysis calc (%) : C 38.55, H 4.31, N 3.75; found: C 38.477 H
4.030 N 3.915
Analysis of 1b
IR(ATR): 1172 cm (m, P-O), 1206 cm-1 (st, P=O).
-1
[
26]
A. L. Spek, Acta. Crystallogr. D. 2009, 65, 148-155.
Elemental analysis calc (%) : C 38.51, H 4.31, N 3.74; found: C 38.557 H
4
.339 N 3.774
Analysis of 1c
IR(ATR): 1164 cm (m, P-O), 1201 cm-1 (st, P=O).
-
1
5
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Coordination polymers based on the
neutral ditopic ligand
(
C
6
H
4
3 2 2
PO(OCH ) ) involving some f-
Block elements
6
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Additional Author information for the electronic version of the article.
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