Communication

pubs.acs.org/crystal

PC Bond Cleavage-Assisted Lanthanide Phosphate Coordination

Polymers
Joydeb Goura, James P. S. Walsh, Floriana Tuna,*, Ritesh Halder, Tapas Kumar Maji,
and Vadapalli Chandrasekhar*,,

Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India

School of Chemistry and Photon Science Institute, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom

Molecular Materials Laboratory, Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientic Research,
Jakkur, Bangalore 560 064, India

National Institute of Science Education and Research, Institute of Physics Campus, Sachivalaya Marg, Sainik School, Bhubaneswar,
Orissa-751 005, India

S Supporting Information
*

ABSTRACT: The reaction of lanthanide(III) salts with an organodiphosphonic

acid under hydrothermal conditions resulted in a PC bond cleavage aording
[{Eu 4 (PO 4 )(PO 4 ) 0 . 5 4 (PO 4 ) 0 . 2 5 4 (H 2 O) 2 }6H 2 O] n (1), [{Dy 4 (PO 4 )(PO4)0.54(PO4)0.254(H2O)2}6H2O]n (2), and [{Gd(PO4)0.5(PO4)0.5(H2O)3}
2H2O]n (3). 1 and 2 are porous 3D coordination polymers whose repeating units
possess a dimeric motif. While one lanthanide ion in the dimer is eight-coordinate in
a distorted square-antiprismatic geometry, the other is nine-coordinate and present
in a distorted monocapped square-antiprismatic geometry. In contrast to 1 and 2, 3
possesses a 2D architecture; the asymmetric unit contains a monomeric GdIII center
which is nine-coordinate in a distorted monocapped square-antiprismatic geometry.

in general, and those containing phosphonate ligands in

particular prompted us to investigate the reactions of
lanthanide salts with a diphosphonic acid. Interestingly, we
nd that under the hydrothermal reaction conditions employed,
a facile PC bond cleavage reaction occurs and generates
lanthanide phosphate coordination polymers. Accordingly, in
this contribution we describe the synthesis and structural
characterization of [{Eu4(PO4)(PO4)0.54(PO4)0.254(H2O)2}
6H 2 O] n , (1), [{Dy 4 (PO 4 )(PO 4 ) 0.54 (PO 4 ) 0.254 (H 2 O) 2 }
6H2O]n (2), and [{Gd(PO4)0.5(PO4)0.5(H2O)3}2H2O]n (3).
To the best of our knowledge these compounds represent the
rst examples of coordination polymers of lanthanide ions built
with phosphate ligands. Magnetic studies have also been carried
out on these compounds which suggest a slow magnetic
relaxation in the DyIII analogue.
The reaction of H5mbpp with lanthanide metal salts
[Ln(NO3)3nH2O, Ln = Eu and Dy (n = 5); Gd (n = 6)]
under hydrothermal conditions aorded the coordination
polymers 13 (Scheme 1). During this reaction an in situ
PC bond hydrolysis occurred and resulted in the formation of
the phosphate ligand, (PO4)3, which enabled the formation of
the coordination polymers. Previously, in the reaction of t-

olynuclear lanthanide complexes have been attracting

considerable attention in recent years in view of their
relevance in catalysis,14 photophysics,57 and magnetism.813
In particular, lanthanide containing compounds are being
studied in considerable detail for their single-molecule813 and
single-ion magnetism behavior.1417 This is because of the large
ground-state spin and high magnetic anisotropy that many
lanthanide ions provide.1822 In contrast to molecular
complexes, coordination polymers containing lanthanide ions
have been much less studied.2328 This is surprising in view of
the considerable interest in transition metal ion-containing
coordination polymers in general,2931 and metalorganic
frameworks (MOFs) in particular. The utility of dicarboxylate
ligands in MOFs has also resulted in their use in lanthanide
chemistry in the assembly of coordination polymers.2328 To
some extent this work has also been extended to phosphonate/
phosphate ligands.3234 We have a long-standing interest in the
use of phosphonate ligands for the preparation of polynuclear
molecular assemblies whose nuclearity can be tuned over a wide
range by the use of synthetic methods that include variation of
the steric bulk on the phosphonate ligand and/or the use of an
ancillary nitrogen ligand.3544 More recently we have started to
engage in the chemistry of polynuclear lanthanide complexes
from a molecular magnetism standpoint.4547 In light of this we
were interested in exploring lanthanide/phosphonate chemistry
and the paucity of lanthanide-containing coordination polymers
XXXX American Chemical Society

Received: November 21, 2014

Revised: March 14, 2015

DOI: 10.1021/cg5017005
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Communication

Crystal Growth & Design

Scheme 1. Synthesis of 1, 2, and 3

BuPO3H2 with FeCl36H2O, a partial PC bond cleavage was

reported in the formation of the molecular complex
[Fe 10 (OH) 8 (HPO 4 )(t-BuPO 3 ) 8 (t-BuPO 3 H) 4 (py) 8 ]4py
5H2O.48 Unlike the latter, which contains both phosphonate
and phosphate ligands, in the current instance the products
contain only phosphate ligands, generating the rst examples of
purely phosphate-bridged 2D and porous 3D lanthanide
cordination polymers. The multidentate coordinating ability
(chelating and/or bridging fashion) of the phosphate ligand
enables it to assemble the coordination polymers readily. It is
interesting to note that, in the absence of the lanthanide metal
ion, the phosphonic acid was not hydrolyzed under the same
hydrothermal reaction conditions (Supporting Information).
Single-crystal X-ray structural studies reveal that compounds
13 crystallize in the monoclinic crystal system (C2/c (1 and
2), P21/n (3)). The crystallographic parameters of these
compounds are given in the Supporting Information.
The overall structural features of 1 and 2 are very similar, and
both compounds are neutral in the crystal structure. The
structure of 2 is described as a respresentative example (Figure
1).

The asymmetric unit of 1 and 2 contains a repeating dimeric

unit. The two lanthanide centers in the dimeric motif are
connected to each other by two bridging phosphate ligands.
One of the bridging phosphate ligands is also involved in a
chelating coordination with one lanthanide center. In addition,
the lanthanide ions contain chelating as well as monodentate
phosphate ligands around them. As a result, a puckered eightmembered ring is formed (Dy2P2O4); the lanthanide ions,
however, are coplanar (SI). Thus, in 2, Dy1 is surrounded by
three 1-, one chelating, and two bridging phosphate ligands in
addition to a water molecule (SI). The other unique lanthanide
center, Dy2, is also surrounded by three chelating, one bridging,
and two 1-phosphate ligands (SI).Thus, Dy1 is eightcoordinate (distorted square-antiprismatic) (Figure 1b) and
Dy2 is nine-coordinate (distorted monocapped square
antiprismatic) (Figure 1c).
The phosphate ligands involved in the dimeric unit extend
the formation of the structure into a three-dimensional
coordination polymer. Viewed in the ab plane the polymeric
network resembles interlinked macrocycles (Figure 1d).
Viewed in the bc plane the structure resembles a layered
B

DOI: 10.1021/cg5017005
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Figure 1. Molecular structure of 2. All of the hydrogen atoms have been omitted for clarity. (b,c) Coordination geometry around the lanthanide
centers. (d) 3D-coordination polymeric structure of 2.

The photoluminescence of 1 and 2 was investigated at room

temperature in the solid state. Complex 1 emits at 427, 561,
588, and 612 nm when excited at 340 nm, although it is wellknown that the characteristic luminescence band of LnIII does
not lie at 427 nm.5053 Coordination polymers of lanthanides
involving oxygen in their local coordination environments have
exhibited such an emission.5053 Based on this, we attribute the
intense emission at 427 nm as being due to an oxide
lanthanide transition. The other peaks at 561, 588, and 612 nm
can be assigned to the transitions of 5D0 7F0, 5D0 7F1, and
5
D0 7F2, respectively (Figure 2).54,55 The presence of the
formally Laporte forbidden 5D0 7F0 transition, along with the
enhanced intensity of the 5D0 7F2 transition, both point to a
reduced symmetry of the europium centers, consistent with the
crystallography studies, which also revealed both eight- and
nine-coordinate environments.

architecture with each pair of layers being interconnected by

bridging phosphate ligands (SI). As a result, a 3D-porous
coordination polymer is formed, the voids of which are
occupied by water molecules. Attempts to replace the water
molcules by other solvent molecules (methanol, ethanol,
acetonitrile, THF) by soaking the crystals into these solvents
were not successful. Such crystalcrystal transformations have
been recently reported.49
The molecular structure of compound 3 is given in Scheme 1
and in the SI. The molecular structure of compound 3 contains
one gadolinium center in the asymmetric unit. This lanthanide
center contains around it two chelating- and two 1phosphates; in addition, three water molecules are also present
in the coordination sphere (SI). Thus, Gd1 is nine-coordinate
(GdO9) in a distorted monocapped square-antiprismatic
geometry (SI).
C

DOI: 10.1021/cg5017005
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Figure 2. Room-temperature solid-state luminescence spectra of 1

(excited at 340 nm).

Upon excitation at 380 nm, compound 2 exhibits

luminescence peaks at 414, 464, 480, and 572 nm. The peaks
at 480 and 572 nm can be assigned to the transitions of 4F9/2
6
H15/2 and 4F9/2 6H13/2, respectively (SI).56,57
A composite of the temperature-dependent magnetic
susceptibilities for compounds 2 and 3 is shown in Figure 3,

Figure 4. N2 adsorption isotherms of compound 1.

Figure 5. CO2 and H2 adsorption isotherms of compound 1.

Figure 3. Temperature dependent magnetic susceptibility of 2 and 3
measured under a static eld of 0.1 T.

might be attributed to the higher diusion barrier of the 1D

channel that restricts the diusion of N2. Surprisingly, at 195 K
it shows type-I uptake prole with nal uptake amount of CO2
of 80 mL g1 (Figure 5). The desorption path is almost
reversible and the isosteric heat of adsorption calculated using
DR equation59 was found to be 28.9 kJmol1 suggesting
appreciable interaction between CO2 and the host framework.
The origin of CO2 selectivity over N2 might be due to the high
quadrupole moment of CO2 that can interact eciently with
the polar pore surface and unsaturated metal sites of the
framework.60,61 At 77 K it also shows H2 uptake of 29 mL g1
(Figure 5).
In summary, we have synthesized the rst examples of
phosphate based 2D- and porous 3D-coordination polymers of
LnIII ions. The formation of these polymers is accompanied by
a metal-assisted PC bond cleavage. While 1 and 2 exhibit an
intense photoluminescence emission band at room temperature
in the solid state, 2 reveals a slow relaxation of magnetization in
the presence of an applied eld.
We thank the Department of Science and Technology, India,
and the Council of Scientic and Industrial Research, India, for
nancial support. V. C. is thankful to the Department of
Science and Technology, for a J. C. Bose fellowship. J. G.
thanks the Council of Scientic and Industrial Research, India,
for a Senior Research Fellowship. J.P.S.W. acknowledges the

and eld-dependent magnetization plots for the same

compounds are given in the Supporting Information. Molar
values are calculated using the crystallographic asymmetric unit.
In compound 2, the room temperature MT value of 28.94 cm3
K mol1 is consistent with two DyIII ions (6H15/2, S = 5/2, L =
5, g = 4/3, C = 14.17 cm3 K mol1). In compound 3, the room
temperature MT value of 7.85 cm3 K mol1 is consistent with
the value expected for a single GdIII ion (8S7/2, S = 7/2, L = 0, g
= 2, C = 7.88 cm3 K mol1).
The MT versus T plot for 3 exhibits essentially no deviation
from the paramagnetic regime from 300 K down to the lowest
temperatures, indicating a lack of exchange interaction between
the GdIII centers. Ac susceptibility measurements of compound
2 reveal a slow relaxation of the magnetization under an applied
eld (SI).
The desolvated framework was obtained by heating the assynthesized compound at 250 C and N2, H2 (at 77 K) and
CO2 (195 K) gas adsorption studies were carried out for
compound 1 and 2 (Figures 4 and 5 and SI). The N2
adsorption measurement of compound 1 at 77 K shows almost
no uptake although the pore sizes are comparable to the kinetic
diameter of N2 (Kinetic diameter 3.64 ) (Figure 4).58 This
D

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North West Nanoscience Doctoral Training Centre at the

University of Manchester for a PhD studentship. We also thank
the EPSRC UK National EPR Research Facility and Service.

ASSOCIATED CONTENT

S Supporting Information
*

Synthetic details, CIF les, additional gures, tables of bond

distance () and bond angle (deg). The Supporting
Information is available free of charge on the ACS Publications
website at DOI: 10.1021/cg5017005.

AUTHOR INFORMATION

Corresponding Authors

*E-mail: oriana.tuna@manchester.ac.uk.
*E-mail: vc@iitk.ac.in; vc@niser.ac.in.
Notes

The authors declare no competing nancial interest.

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