Coordination polymers constructed from a tripodal phosphoryl carboxylate ligand: Synthesis, structures and physical properties

Article abstract of DOI:10.1039/c5ce00430f

By employment of a new tripodal phosphoryl carboxylate ligand, tris(p-carboxyl-biphenyl)phosphine oxide (H₃TBPPO), four novel coordination polymers, namely, Zn₃(TBPPO)₂ (1), Cd₃(TBPPO)₂ (2), Co_3<

Full text of DOI:10.1039/c5ce00430f

View Article Online
View Journal
CrystEngComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Y. Yang, Z. Lin,
J. Liang, Y. Huang and R. Cao, CrystEngComm, 2015, DOI: 10.1039/C5CE00430F.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/crystengcomm

Page 1 of 8
CrystEngComm
View Article Online
DOI: 10.1039/C5CE00430F
Journal Name
RSCPublishing
ARTICLE
Coordination polymers constructed from a tripodal
phosphoryl carboxylate ligand: synthesis, structures
and physical properties
Cite this: DOI: 10.1039/x0xx00000x
Yan-Yan Yang, a, b Zu-Jin Lin,*a Jun Liang, a, c Yuanbiao Huanga and Rong Cao*a
Received 00th January 2012,
Accepted 00th January 2012
By employment of
biphenyl)phosphine oxide (H3TBPPO), four novel coordination polymers, namely, Zn3(TBPPO)
), Cd3(TBPPO)2 ), Co3(TBPPO)2 ) and In(TBPPO) ( ), have been synthesized and
characterized. Complexes and are isostructural. The crystal structure analysis reveals
a new tripodal phosphoryl carboxylate ligand, tris(pꢀcarboxylꢀ
DOI: 10.1039/x0xx00000x
www.rsc.org/
(
1
(
2
(
3
4
2
1
,
2
3
that complexes 1-3 consist of trinuclear metal building units, which are further bridged by the
tripodal phosphine oxide carboxylate ligands to give a (4,8)ꢀconnected 2ꢀfold interpenetrating
flu topological net with point symbol of (412·612·84)(46)2, while complex
4
possesses a 3D 4ꢀ
fold interpenetrating dia network with point symbol of (66). Luminescence measurements
indicate that complexes and all show strong emission bands at around 378 nm in the
solid state at room temperature. Furthermore, the temperatureꢀdependent magnetic
susceptibility study shows that complex exhibits antiferromagnetism property.
1
,
2
4
3
Introduction
Experimental Section
Coordination polymers (CPs) have attracted enormous
2
interest due to their intriguing structural topologies,1, and
Materials and General Methods
potential applications in diverse areas, such as luminescence,3ꢀ5
gas adsorption and separation,6ꢀ8 nonlinear optics,9 catalysis,10,
All commercially purchased chemicals are of reagent grade
quality and used as received without further purification. C, H
drug delivery,12, 13 proton conduction14 etc. CPs are made up
11
of metal ions or metal clusters (as nodes) and organic ligands
(as spacers). The rational choice of ligands plays significant
role in the final framework structure and properties.1, 15, 16
Among various ligands, multifunctional carboxylate
organic ligands have been utilized to construct CPs with novel
structures and diverse applications as functional materials.
Particularly, carboxylate ligands bearing high C3 symmetry
have been intensively studied,17ꢀ23 which show great advantages
over those ligands with low symmetry in constructing novel
CPs.
As one type of C3 symmetry ligand, tris(pꢀ
carboxylphenyl)phosphine oxide (TPO) has received increasing
attention, because the ligand not only possess three C3
symmetrical benzoates, but also has one more coordination
atom O of the P=O, which can impose great influence on the
synthesized material. Based on TPO ligand, some CPs with
interesting properties such as gas separation, luminescence have
been designed and constructed.24ꢀ37 Inspired by the fruitful
research results concerning on H3TPO, we extend the ligand
and N analyses were recorded with a Vario MICRO EL
Ⅲ
elemental analyzer instrument. Infrared (IR) spectra were
carried out on PerkinElmer Spectrum instrument with KBr
pellets. Thermogravimetric analyses (TGA) were performed on
an SDT Q600 thermogravimetric instrument with a heating rate
of 10
ray diffraction (PXRD) patterns were recorded on a Rigaku
MiniFlex2 diffractometer with CuꢀKα radiation ( = 1.54056Å )
℃
minꢀ1 under a flowing nitrogen atmosphere . Powder Xꢀ
λ
at room temperature. The solid–state photoluminescent
excitation and emission spectra were collected at room
temperature on an Edinburgh FLS920 fluorescence
spectrometer with an Edinburgh Xe900 xenon arc lamp as the
light source. The absolute quantum yields for these samples
were measured at room temperature. They were measured by
using a barium sulfate coated integrating sphere (Edinburgh) as
the sample chamber, which then was mounted on the
fluorimeter (FLS920); at the same time, the entry and output
H3TPO
oxide(H3TBPPO) ligand to elaborately build new CPs. Herein,
four new CPs formulated as Zn3(TBPPO)2 ( ), Cd3(TBPPO)2
), Co3(TBPPO)2 and In(TBPPO) have been
to
tris(pꢀcarboxylꢀbiphenyl)phosphine
port of the sphere were located at a 90
°geometry from each
1
other in the plane of the spectrometer. The magnetic
measurement was performed with a Quantum Design SQUID
(
2
(
3
)
(4)
successfully constructed. The synthesis, crystal structures and
physical properties of these complexes are discussed.
MPMSꢀXL. The single crystal sample
3 was placed in a gel
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 1

CrystEngComm
Page 2 of 8
VJieowuArrtnicalelONnlainme e
ARTICLE
DOI: 10.1039/C5CE00430F
capsule sample holder and then it was suspended in a plastic mixture was allowed to reflux for 2 days at 80
℃
under nitrogen
drinking straw. Magnetic susceptibility was measured at a atmosphere. After cooling to room temperature, the reaction
temperature scan rate of 2 K min−1 in the temperature range of mixture was extracted with mixed solvent of water and ethyl
300K to 2 K at 1000 Oe.
acetate (3 × 10 mL) and the organic phase was dried with
sodium sulfate. After removing the solvent using a rotary
evaporator, the crude product was purified by column
chromatography on silica gel with ethyl acetate/petroleum ether
(v/v = 1:6) to give compound TMBPPO as a white solid
(411.5mg, 0.75 mmol, 75% yield based on TBrPPO).
Synthesis of H3TBPPO ligands
1H NMR (400 MHz, CDCl3) δ 7.82 (m, 6H), 7.72 (d, 6H), 7.54
(d, 6H), 7.29 (d, 9H), 2.43 (s, 9H); 13C NMR (101 MHz, CDCl3)
δ 144.68, 138.13, 137.06, 132.61, 130.37, 129.69, 127.12,
127.00, 21.15; 31P NMR (162 MHz, CDCl3) δ 28.93 (s).
HRꢀMS (ESI): m/z calcd for TMBPPO [M + H]+ 549.2342,
found 549.2346. Elemental analysis (EA) for TMBPPO (%):
Calcd: C, 85.38; H, 6.06. Found (%): C, 86.03; H, 6.40.
Synthesis of tris(p-carboxyl-biphenyl)phosphine oxide
(H3TBPPO)
Scheme
1 Strategy for the synthesis of H3TBPPO ligand.
A mixture of TMBPPO (176.00 mg, 0.32 mmol), pyridine (150
mL) and H2O (100 mL) was added to a 500 mL schlenk flask
equipped with mechanical stirring device. The mixture was
Synthesis of Tris(
(TBrPPO)
p-bromophenyl)phosphine oxide
allowed to reflux for 2 days at 100
℃, to which potassium
permanganate (330.00 mg, 2.08 mmol) was added in batches
during the reflux process. After cooling to room temperature,
the reaction mixture was filtered under vacuum, and then the
filtrate was evaporated in vacuo. The residue was acidified with
6 M HCl to yield white precipitate of H3TBPPO, which was
filtered, washed with water, and dried under vacuum (178.8
mg, 0.28 mmol, 88% yield based on TMBPPO). 1H NMR (400
MHz, DMSO) δ 13.09 (s, 3H), 8.06 (d, 6H), 7.96 (d, 6H), 7.88
(d, 6H), 7.82 (d, 6H); 13C NMR (101 MHz, DMSO) δ 167.48,
143.46, 143.03, 133.11, 132.79, 132.09, 130.92, 130.53,
127.91, 127.71; 31P NMR (162 MHz, DMSO) δ 25.02 (s).
HRꢀMS (ESI): m/z calcd for H3TBPPO [M ꢀ H]ꢀ 637.1422,
found 637.1422. Elemental analysis (EA) for H3TBPPO (%):
Calcd: C, 73.35; H, 4.26. Found (%): C, 73.40; H, 4.32.
A solution of
23.3 mmol) in freshly distilled THF (16 mL) was added
dropwise to a solution of ꢀdibromobenzene (5g, 17.0 mmol) in
freshly distilled THF (30 mL) at ꢀ78 . When the addition was
completed, POCl3 (0.6 mL, 7.1 mmol) in freshly distilled THF
(30 mL) was charged into the mixture at ꢀ78 over a period of
3 h. The reaction mixture was allowed to warm to room
temperature, and then stirring was continued for 12 h.
Afterwards, the reaction mixture was extracted with a saturated
nꢀBuLi (15% in hexane, 1.6 mol/L) (14.5 mL,
p
℃
℃
aqueous solution of NH4Cl (50 mL) and nꢀhexane (50 mL). The
organic phase was collected and dried over Na2SO4 before
evaporated in vacuo. The yellow residue was purified by
column chromatography on silica gel with ethyl
acetate/petroleum ether (v/v = 1:6) to give compound TBrPPO
as a white solid (2.2 g, 4.2 mmol, 60% yield based on POCl3).
1H NMR (400 MHz, CDCl3) δ 7.65 (m, 6H), 7.50 (m, 6H); 13C
NMR (101 MHz, CDCl3) δ 133.40 (d), 132.12 (d), 131.17 (d),
130.08 (s), 127.84 (m); 31P NMR (162 MHz, CDCl3) δ 27.46
(s). HRꢀMS (ESI): m/z calcd for TBrPPO [M + Na]+ 534.8068,
found 534.8063. Elemental analysis (EA) for TBrPPO (%):
Calcd: C, 41.98; H, 2.35. Found(%): C, 42.05; H, 2.40.
Synthesis of compounds 1-4
Synthesis of M3(TBPPO)2 [M=Zn (1), Cd (2) and Co (3)]
A mixture of nitrate salt [Zn(NO3)2·6H2O (
), or Co(NO3)2·6H2O ( )] (0.06 mmol), H3TBPPO (6 mg,
0.01 mmol) and concentrated HNO3 (150 L) was added to a
1), Cd(NO3)2·4H2O
(
2
3
u
mixed solvent of DMA (1 mL) and distilled water (1 mL) in a
20 mL stainless glass vial. The mixture was ultrasonicated for
20 min and heated at 120 C for 3 days, and then cooled to
Synthesis of tris(
(TMBPPO)
p-methyl-biphenyl)phosphine oxide
o
room temperature.
TBrPPO (515.0 mg, 1 mmol), 4ꢀmethylbenzeneboronic acid
(608.4 mg, 4.5 mmol), potassium carbonate (1658.5 mg, 12
mmol) and tetrakis(triphenylphosphine)palladium (57.8 mg,
0.05 mmol) were charged into a 250 mL schlenk flask protected
by nitrogen gas. Then 20 mL degassed solvent ethanol and 20
mL degassed toluene were introduced into the system. The
For 1: Colorless blockꢀshaped large crystals were collected in
80% yield based on H3TBPPO. Elemental analysis (EA) for
C78H48O14P2Zn3 (%): Calcd: C, 63.85; H, 3.30. Found: C, 64.20;
H, 3.96. IR (KBr, cmꢀ1 ): 3436 (m), 3046 (m), 2774 (w), 2619
(w), 1923 (w), 1807 (w), 1706 (m), 1601 (s), 1544 (s), 1391 (s),
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 8
Journal Name
CrystEngComm
View ArticAle ROnTliInCeLE
DOI: 10.1039/C5CE00430F
1275 (w), 1201 (s), 1115 (s), 991 (s), 960 (w), 839 (m), 765 (s),
698 (m), 638 (s), 571 (s), 452 (w), 360 (m).
For 2: Colorless blockꢀshaped crystals were collected in 70%
yield based on H3TBPPO. Elemental analysis (EA) for
C78H48O14P2Cd3 (%): Calcd: C, 58.25; H, 3.01. Found (%): C,
59.02; H, 3.45. IR (KBr, cmꢀ1): 3441 (w), 3031 (w), 2605 (w),
1920 (w), 1814 (w), 1705 (s), 1595 (s), 1536 (s), 1390 (s), 1267
(w), 1176 (m), 1112 (s), 1076 (w), 988 (m), 841 (m), 766 (s),
708 (m), 632 (w), 568 (s), 387 (w).
For 3: Dark violet block crystals of 3 were collected in 70%
yield based on H3TBPPO. Elemental analysis (EA) for
C78H48O14P2Co3 (%): Calcd: C, 64.70; H, 3.34. Found (%): C,
63.93; H, 3.81. IR (KBr, cmꢀ1): 3437 (s) 3453 (w), 3030 (w),
1916 (w), 1797 (w), 1722 (m), 1584 (s), 1521 (s), 1404 (s),
1196 (m), 1112 (m), 986 (m), 839 (m), 762 (s), 691 (w), 566 (s),
449 (w), 419 (w), 359 (m).
Synthesis of In(TBPPO) (4)
A mixture of In(NO3)3 (18.0 mg, 0.06 mmol), H3TBPPO (6 mg,
0.01 mmol), concentrated HNO3 (200 uL), distilled water (1
mL) and DMA (1 mL) was sealed in a 20 mL stainless glass
vial. The mixture was ultrasonicated for 20 min and heated at
Scheme 2 Coordination modes of H3TBPPO ligand.
o
100 C for 3 days. After cooling to room temperature, colorless
crystals of
4 were collected in 80% yield based on H3TBPPO.
Results and discussion
Elemental analysis (EA) for C39H24O7PIn (%): Calcd: C, 62.42;
H, 3.22. Found: C, 62.41; H, 3.93. IR (KBr, cmꢀ1 ): 4073 (w),
3437 (w), 3052 (m), 2940 (w), 2790 (w), 2620 (w), 2488 (w),
1917 (m), 1820 (w), 1713 (s), 1605 (s), 1507 (s), 1404 (s), 1229
(s), 1162 (m), 1114 (m), 989 (s), 882 (s), 784 (w), 696 (w), 568
(s), 401 (w), 357 (m).
Description of the crystal structures
Crystal structures of M3(TBPPO) 2 [M=Zn (1), Cd (2) and Co (3)]
Singleꢀcrystal Xꢀray diffraction studies reveal that complexes
1-3 are 3D frameworks, crystallizing in the cubic system, with
the space group Iaꢀ3. Because they are isostructural, herein,
only the structure of
representative. Each asymmetric unit of
1
will be described in detail as a
contains three
Single-Crystal X-ray Crystallography
1
Singleꢀcrystal Xꢀray diffraction data of compounds 1-4 were
collected on a SuperNova CCDꢀbased diffractometer equipped
with graphiteꢀmonochromated CuꢀKα radiation by using the
scan at 100 K. All of the structures were solved by direct
methods and refined on F2 by full matrix leastꢀsquares using the
SHELXLꢀ97 program package. All nonꢀhydrogen atoms were
refined with anisotropic thermal parameters. The hydrogen
atoms attached to carbon atoms were added theoretically.
Detailed final refinements and structure data of these
compounds are presented in Table 1.
crystallographically independent zinc ions and two TBPPO3ꢀ
ligands. The coordination mode of H3TBPPO ligand is shown
in Scheme 1a. In the structure, one of the crystallographically
independent zinc ion (Zn1) is octahedrally coordinated by six
oxygen atoms from six separate bridging carboxyl groups (O1,
O1B, O1C, O1D, O1E, O1G); the other zinc ion (Zn2) is four
coordinated by three separate bridging carboxyl groups (O2,
O2B, O2D) and one oxygen atom (O3F) from the P=O of the
fourth ligand (Figure 1). The three adjacent zinc centers are
bridged by six carboxylate groups from six TBPPO3ꢀ ligands,
three between each pair, in bisꢀbridging fashion, leading to the
construction of a trinuclear zinc cluster Zn3(COO)6. Considering
the trinuclear Zn3(COO)6 building units as 8ꢀconnected nodes
and the TBPPO 3ꢀ ligands as 4ꢀconnected nodes, the structure of
ωꢀ
1
can be viewed as a 3D twoꢀfold interpenetrating 4,8ꢀ
connected binodal flu net with point symbol of (412·612·84)(46)2
(Fig 2, Fig.3). The ZnꢀO bond lengths range from 1.895 to
2.075 Å, which are comparable with values of other reported
zincꢀoxygen donor complexes.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

CrystEngComm
Page 4 of 8
ARTICLE
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C5CE00430F
Table 1 Crystallographic data for 1-4
Compound
Chemical formula
Formula Mass
Crystal system
a/Å
1
2
3
4
C78H48O14P2Zn3
1467.21
cubic
C78H48O14P2Cd3
1608.30
cubic
C78H48O14P2Co3
1447.89
cubic
C39H24O7PIn
750.37
cubic
23.3664(3)
23.3664(3)
23.3664(3)
90.00
23.7697(4)
23.7697(4)
23.7697(4)
90.00
23.3991(4)
23.3991(4)
23.3991(4)
90.00
23.5428(2)
23.5428(2)
23.5428(2)
90.00
b/Å
c/Å
α(°)
β(°)
90.00
90.00
90.00
90.00
γ(°)
90.00
90.00
90.00
90.00
Unit cell volume/ Å3
12757.8(3)
173(2)
Iaꢀ3
13429.8(4)
173(2)
Iaꢀ3
12811.4(4)
173(2)
Iaꢀ3
13048.92(19)
173(2)
Iꢀ43d
T/K
Space group
Z
8
8
8
16
ꢁ/mmꢀ1
2.378
8.552
7.072
6.686
Data measured
Unique data
Rint
R1a (I>2σ(I))
wR(F2)b (I>2σ(I))
5643
5746
5020
4856
2085
2193
2093
1755
0.0206
0.0703
0.2264
0.0867
0.2576
1.065
0.0279
0.0967
0.2967
0.1314
0.3380
1.174
0.0487
0.0892
0.2700
0.1747
0.3250
1.056
0.0286
0.0578
0.1555
0.0668
0.1702
1.180
a
R1 (all data)
wR(F2)b (all data)
Goodness of fit on F2
CCDC number
1046861
1046862
1046863
1046864
aR1 = Σ||Fo| ꢀ |Fc||/Σ|Fo|. bwR2 = {Σ[w(Fo2 ꢀ Fc2)2/Σ[wFo2]2]}1/2
.
Fig. 1 The coordination environment of the central Zn (
Ⅱ
) ions in
1
with 30%
probability of thermal ellipsoids. Hydrogen atoms are omitted for clarity.
Symmetry codes: A, z- 1/2, 1- x, y; B, 1-z, 1/2 + x, 3/2 - y; C, z- 1/2, 1-x, y; D, y -
1/2, 3/2 – z, 1-x; E, 1 - y, z, 1/2 + x; F, 1/2 - y , 1-z, 1/2 + x; G, 1/2 - x, 3/2 - y, 3/2 –
z; H, y, 1/2 + z, 1-x; I, z, x, y; J, y, z, x.
Figure 2 Two-fold interpenetrating flu net topology of 1.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 8
Journal Name
CrystEngComm
View ArticAle ROnTliInCeLE
DOI: 10.1039/C5CE00430F
Fig. 5 4-fold interpenetrating dia net of
4
Figure 3 Two-fold interpenetrating framework of 1.
Crystal structure of In(TBPPO) (4)
Singleꢀcrystal Xꢀray diffraction study showed that that complex
crystallizes in the cubic system, with the space group ꢀ43d.
4
I
As shown in Fig. 4, the central indium ion (In1) is coordinated
by six oxygen atoms (O2, O2A, O2B, O3, O3A, O3B) from
three carboxylate groups of three individual H3TBPPO ligands,
as well as one oxygen atom (O1) from the P=O of the fourth
ligand, composing a monocapped octahedron geometry with Inꢀ
O bond lengths ranging from 2.086 Å to 2.234 Å. The
coordination mode of the carboxylic group of the H3TBPPO
ligand is shown in Scheme 1b. From the topological viewpoint,
the metal centers and the ligands can both be seen as distorted
tetrahedral 4ꢀconnected nodes. They connect to each other to
produce an infinite 3D 4ꢀfold interpenetrating dia network with
point symbol of (66) (Fig. 5, Fig. 6).
Fig. 6 4-fold interpenetrating framework of
4
To investigate the purity and homogeneity of the bulk materials
of compounds 1-4, the asꢀsynthesized samples of the four
complexes were measured by power Xꢀray diffraction (PXRD)
at room temperature. As shown in Fig. S8ꢀS11, the peak
positions of the experimental patterns are in good agreement
with those calculated from singleꢀcrystal Xꢀray diffraction data,
which obviously suggest the good purity and homogeneity of
these samples. To explore their thermal stabilities,
thermogravimetric analyses (TGA) were performed on a STQ
600 instrument. As shown in Fig. S12, compounds 1ꢀ4 show
similar thermal stabilities. Because they contain no solvent
molecules in the crystal lattice, significant weight losses are
observed only after 400
℃ , corresponding to the structural
decomposition of the coordination polymers.
Photoluminescence properties
Luminescent properties of complexes constructed from d10
metal ions have gained immense attention due to their extensive
applications in lightꢀemitting devices, chemical sensors,
Fig. 4 The coordination environment of the central In (
Ⅲ) ion in 4 with 30%
39
photophysical devices, optoelectronic devices etc 38,
.
probability of thermal ellipsoids. Hydrogen atoms are omitted for clarity.
Symmetry codes: A, z, x, y; B, y, z, x; C, z- 1/2, 3/2 - x, 1 - y; D, 1 - y, z - 1/2, 3/2 - x;
E, 3/2 - x, 1 - y, z - 1/2.
Therefore, the photoluminescence properties of complexes
1, 2
and as well as the free ligand H3TBPPO have been
4
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 5

CrystEngComm
Page 6 of 8
ARTICLE
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C5CE00430F
investigated at room temperature in the solid state. As shown in
Figure 7, the free H3TBPPO ligand shows photoluminescence
at ca. 398 nm when excited at 350 nm, which may be ascribed
to the π*−n or π*−π electron transition.27, 40 Upon excitation at
345 nm, 340 nm, and 340 nm, the similar emission bands at ca
.
378 nm were observed in complexes , and . Because the
1
,
2
4
central metal ions Zn2+, Cd2+, and In3+ are not apt to be oxidized
or reduced owing to their d10 configuration, the emissions of
these complexes are neither metalꢀtoꢀligand charge transfer
(MLCT) nor ligandꢀtoꢀmetal charge transfer (LMCT), which
can probably be attributed to the intraligand or ligandꢀtoꢀligand
charge transfer.41ꢀ45 Besides, compared with the free H3TBPPO
ligand, the enhancement of the emissions for 1, 2 and 4 may be
assigned to the increase of the ligand conformation rigidity
owing to their coordination with metal ions, resulting in a
decrease in the nonradiative decay of intraligand excited
states.27, 46, 47 Furthermore, the small blue shift in the emission
Fig. 8 Temperature dependence of the magnetic susceptibility of compound
Inset: temperature dependence of χmT vs. T.
3.
spectra maximum for compounds 1, 2 and 4 may be associated
with the perturbation caused by the metal coordination.48 It is
worthy to note that the luminescent quantum yield of
compounds 1, 2 and
respectively, which is moderate compared to some reported
CPs.28, 49 The photoluminescence properties of compounds 1, 2
4 is up to 53.31%, 49.02% and 57.31%,
Conclusions
In this work, four coordination polymers formulated as
Zn3(TBPPO)2
In(TBPPO) (
(
1
), Cd3(TBPPO)2
(2), Co3(TBPPO)2 (3) and
and
4 suggest that these complexes can be potential candidates
4
) have been successfully synthesized under
for organicꢀinorganic hybrid luminescent materials.
solvothermal conditions based on a new tripodal phosphoryl
carboxylate H3TBPPO ligand. Complexes and are
1
,
2
3
isostructural, all of them consist of trinuclear metal building
units, and show a (4, 8)ꢀconnected 2ꢀfold interpenetrating flu
topological net, while complex
interpenetrating dia network. Luminescence measurements
indicate that complexes and all show strong emission
4 possesses a 3D 4ꢀfold
1
,
2
4
bands at around 378 nm which are mainly dominated by the
ligand. Remarkably, the luminescent quantum yield of
compounds 1, 2 and
4 is up to 53.31%, 49.02% and 57.31%,
respectively. Besides, complex
property.
3 exhibits antiferromagnetism
Acknowledgements
We thank the financial support from the 973 Program
(2011CB932504 and 2014CB845605), NSFC (21331006,
21303205, 21273238 and 21221001), Natural Science
Foundation of Fujian Province of China (2014J05020). We also
thank Prof. JinꢀShun Huang, Prof. JiuꢀTong Chen and Prof.
XiaoꢀYing Huang for the crystal structural refinements.
Fig. 7 The solid-state photoluminescence spectra for compounds 1, 2, 4 and the
free H3TBPPO ligand.
Magnetic properties
Temperature dependence of the magnetic susceptibility at 2ꢀ
300 K in a field of 1000 Oe was investigated for magnetic ions
Notes and references
containing compound
χmꢀ1, and χm T versus T plots in Figure 8. The experimental χm
T product of
at 300K is 8.53 cm3 molꢀ1 K, it continuously
decreases to 2.19 cm3 molꢀ1 K as the temperature is lowered to
K. The temperature dependence of the reciprocal
susceptibilities (χmꢀ1) of
follows the CurieꢀWeiss law above
3. The magnetic data are shown as χm,
a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of
Matter, University of Chinese Academy of Sciences, Fujian, Fuzhou, 350002, P.R. China. Eꢀ
mail: rcao@fjirsm.ac.cn; linzujin@fjirsm.ac.cn; Fax: (+86) 591ꢀ8379ꢀ6710; Tel: (+86) 591ꢀ
8379ꢀ6710.
3
2
3
b College of Chemistry, Fuzhou University,Fuzhou,350002, China.
50 K, giving a Weiss constant θ = −45.7 K and a Curie constant
C = 9.67 cm3 mol−1 K, which indicates the presence of
antiferromagnetic interactions between adjacent Co(II) ions.50ꢀ52
c College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 7 of 8
Journal Name
CrystEngComm
View ArticAle ROnTliInCeLE
DOI: 10.1039/C5CE00430F
Hwang, J.ꢀS. Chang and S. M. Humphrey, Chem. Commun., 2011,
47, 4899ꢀ4901.
Electronic Supplementary Information (ESI) available: powder Xꢀray
diffraction, thermogravimetric analysis and IR spectra. See DOI:
10.1039/x0xx00000x.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
S. M. Humphrey, S. E. Oungoulian, J. W. Yoon, Y. K. Hwang, E.
R. Wise and J.ꢀS. Chang, Chem. Commun., 2008, 2891ꢀ2893.
M. John Plater, M. R. St. J. Foreman, E. Coronado, C. J. Gomezꢀ
Garcia and A. M. Z. Slawin, Dalton Trans., 1999, 4209ꢀ4216.
M. John Plater, M. S. Foreman and J. S. Skakle, J Chem.
Crystallogr., 2000, 30, 449ꢀ453.
M. J. Plater, M. S. J. Foreman, T. Gelbrich and M. Hursthouse, J
Chem. Crystallogr., 2000, 30, 155ꢀ158.
Q. H. Chen, F. Y. Lian, F. L. Jiang, L. Chen and M. C. Hong,
Inorg. Chim. Acta, 2012, 392, 396ꢀ403.
P. Schmiedel and H. Krautscheid, Z. Anorg. Allg. Chem., 2012,
638, 1839ꢀ1848.
Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev., 2011, 112, 1126ꢀ
1162.
R. Flamholc, D. Plazuk, J. Zakrzewski, R. Metivier, K. Nakatani,
A. Makal and K. Wozniak, RSC Adv., 2014, 4, 31594ꢀ31601.
L.ꢀP. Zhang, J.ꢀF. Ma, J. Yang, Y.ꢀY. Pang and J.ꢀC. Ma, Inorg.
Chem., 2010, 49, 1535ꢀ1550.
L. Wen, Y. Li, Z. Lu, J. Lin, C. Duan and Q. Meng, Cryst. Growth
Des., 2005, 6, 530ꢀ537.
L. Wen, Z. Lu, J. Lin, Z. Tian, H. Zhu and Q. Meng, Cryst.
Growth Des., 2006, 7, 93ꢀ99.
J.ꢀG. Lin, S.ꢀQ. Zang, Z.ꢀF. Tian, Y.ꢀZ. Li, Y.ꢀY. Xu, H.ꢀZ. Zhu and
Q.ꢀJ. Meng, CrystEngComm, 2007, 9, 915.
J.ꢀP. Collin, I. M. Dixon, J.ꢀP. Sauvage, J. A. G. Williams, F.
Barigelletti and L. Flamigni, J. Am. Chem. Soc., 1999, 121, 5009ꢀ
5016.
X. Zhao, X. Wang, S. Wang, J. Dou, P. Cui, Z. Chen, D. Sun, X.
Wang and D. Sun, Cryst. Growth Des., 2012, 12, 2736ꢀ2739.
S.ꢀL. Zheng, J.ꢀH. Yang, X.ꢀL. Yu, X.ꢀM. Chen and W.ꢀT. Wong,
Inorg. Chem., 2003, 43, 830ꢀ838.
Z. Lin, X. Lin and R. Cao, Acta Chim. Sinica, 2012, 70, 2012.
H. Zhang, L. Zhou, J. Wei, Z. Li, P. Lin and S. Du, J. Mater.
Chem., 2012, 22, 21210.
T. Fiedler, M. Hilder, P. C. Junk, U. H. Kynast, M. M. Lezhnina
and M. Warzala, Eur. J. Inorg. Chem., 2007, 2007, 291ꢀ301.
Z.ꢀB. Han, J.ꢀW. Ji, H.ꢀY. An, W. Zhang, G.ꢀX. Han, G.ꢀX. Zhang
and L.ꢀG. Yang, Dalton Trans., 2009, 9807ꢀ9811.
L.ꢀF. Ma, Y.ꢀY. Wang, L.ꢀY. Wang, D.ꢀH. Lu, S. R. Batten and J.ꢀG.
Wang, Cryst. Growth Des., 2009, 9, 2036ꢀ2038.
1.
2.
M. Eddaoudi, D. F. Sava, J. F. Eubank, K. Adil and V. Guillerm,
Chem. Soc. Rev., 2015, 44, 228ꢀ249.
T.ꢀF. Liu, D. Feng, Y.ꢀP. Chen, L. Zou, M. Bosch, S. Yuan, Z. Wei,
S. Fordham, K. Wang and H.ꢀC. Zhou, J. Am. Chem. Soc., 2014,
137, 413ꢀ419.
3.
4.
Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev., 2014, 43, 5815ꢀ
5840.
Z. Wei, Z.ꢀY. Gu, R. K. Arvapally, Y.ꢀP. Chen, R. N. McDougald,
J. F. Ivy, A. A. Yakovenko, D. Feng, M. A. Omary and H.ꢀC. Zhou,
J. Am. Chem. Soc., 2014, 136, 8269ꢀ8276.
5.
Y.ꢀY. Yang, Z.ꢀJ. Lin, T.ꢀT. Liu, J. Liang and R. Cao,
CrystEngComm, 2015, 17, 1381ꢀ1388.
6.
Z.ꢀJ. Lin, T.ꢀF. Liu, Y.ꢀB. Huang, J. Lu and R. Cao, Chem.ꢀEur. J.,
2012, 18, 7896ꢀ7902.
7.
Y. Huang, Z. Lin, H. Fu, F. Wang, M. Shen, X. Wang and R. Cao,
ChemSusChem, 2014, 7, 2647ꢀ2653.
8.
Z. J. Lin, Y. B. Huang, T. F. Liu, X. Y. Li and R. Cao, Inorg.
Chem., 2013, 52, 3127ꢀ3132.
9.
J. Yu, Y. Cui, C. Wu, Y. Yang, Z. Wang, M. O'Keeffe, B. Chen and
G. Qian, Angew. Chem., Int. Ed., 2012, 51, 10542ꢀ10545.
T. Uemura, R. Kitaura, Y. Ohta, M. Nagaoka and S. Kitagawa,
Angew. Chem. Int. Ed., 2006, 45, 4112ꢀ4116.
J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C.ꢀY. Su, Chem.
Soc. Rev., 2014, 43, 6011ꢀ6061.
R. C. Huxford, K. E. deKrafft, W. S. Boyle, D. Liu and W. Lin,
Chem. Sci., 2012, 3, 198ꢀ204.
K. M. L. TaylorꢀPashow, J. D. Rocca, Z. Xie, S. Tran and W. Lin,
J. Am. Chem. Soc., 2009, 131, 14261ꢀ14263.
P. Ramaswamy, N. E. Wong and G. K. Shimizu, Chem. Soc. Rev.,
2014, 43, 5913ꢀ5932.
Z.ꢀJ. Lin, J. Lu, M. Hong and R. Cao, Chem. Soc. Rev., 2014, 43,
5867ꢀ5895.
D. J. Tranchemontagne, J. L. MendozaꢀCortes, M. O'Keeffe and O.
M. Yaghi, Chem. Soc. Rev., 2009, 38, 1257ꢀ1283.
Z. Wang, K. K. Tanabe and S. M. Cohen, Inorg. Chem., 2008, 48,
296ꢀ306.
D. Yuan, D. Zhao, D. Sun and H. C. Zhou, Angew. Chem. Int. Ed.,
2010, 49, 5357ꢀ5361.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
45.
46.
47.
48.
49.
50.
51.
52.
Y. Xu, D. Yuan, B. Wu, L. Han, M. Wu, F. Jiang and M. Hong,
Cryst. Growth Des., 2006, 6, 1168ꢀ1174.
J. Kim, B. Chen, T. M. Reineke, H. Li, M. Eddaoudi, D. B. Moler,
M. O'Keeffe and O. M. Yaghi, J. Am. Chem. Soc., 2001, 123,
8239ꢀ8247.
20.
21.
22.
S. J. Garibay, J. R. Stork, Z. Wang, S. M. Cohen and S. G. Telfer,
Chem. Commun., 2007, 4881ꢀ4883.
K. Koh, A. G. WongꢀFoy and A. J. Matzger, Angew. Chem.Int. Ed.,
2008, 47, 677ꢀ680.
O. K. Farha, A. O. Yazaydin, I. Eryazici, C. D. Malliakas, B. G.
Hauser, M. G. Kanatzidis, S. T. Nguyen, R. Q. Snurr and J. T.
Hupp, Nat. Chem., 2010, 2, 944ꢀ948.
23.
24.
Y. Yan, S. Yang, A. J. Blake, W. Lewis, E. Poirier, S. A. Barnett, N.
R. Champness and M. Schroder, Chem. Commun., 2011, 47, 9995ꢀ
9997.
I. A. Ibarra, T. W. Hesterberg, J. S. Chang, J. W. Yoon, B. J.
Holliday and S. M. Humphrey, Chem. Commun., 2013, 49, 7156ꢀ
7158.
25.
26.
27.
28.
29.
30.
31.
W. R. Lee, D. W. Ryu, J. W. Lee, J. H. Yoon, E. K. Koh and C. S.
Hong, Inorg. Chem., 2010, 49, 4723ꢀ4725.
W. R. Lee, D. W. Ryu, W. J. Phang, J. H. Park and C. S. Hong,
Chem. Commun., 2012, 48, 10847ꢀ10849.
X. J. Li, F. L. Jiang, M. Y. Wu, L. Chen, J. J. Qian, K. Zhou, D. Q.
Yuan and M. C. Hong, Inorg. Chem., 2014, 53, 1032ꢀ1038.
Z. J. Lin, Z. Yang, T. F. Liu, Y. B. Huang and R. Cao, Inorg.
Chem., 2012, 51, 1813ꢀ1820.
I. A. Ibarra, J. W. Yoon, J.ꢀS. Chang, S. K. Lee, V. M. Lynch and S.
M. Humphrey, Inorg. Chem., 2012, 51, 12242ꢀ12247.
I. A. Ibarra, T. W. Hesterberg, B. J. Holliday, V. M. Lynch and S.
M. Humphrey, Dalton Trans., 2012, 41, 8003ꢀ8009.
A. M. Bohnsack, I. A. Ibarra, P. W. Hatfield, J. W. Yoon, Y. K.
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 7

CrystEngComm
Page 8 of 8
View Article Online
DOI: 10.1039/C5CE00430F
Coordination polymers constructed from a tripodal phosphoryl
carboxylate ligand: synthesis, structures and physical properties
Yan-Yan Yang, a, b Zu-Jin Lin,*a Jun Liang, a, c Yuanbiao Huanga and Rong
Cao*a
a State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences,
Fujian, Fuzhou,350002, P.R. China. E-mail: rcao@fjirsm.ac.cn; Fax: (+86) 591-8379-6710; Tel: (+86) 591-8379-6710.
b College of Chemistry, Fuzhou University,Fuzhou,350002, China.
c College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China
Four coordination polymers based on a new tripodal phosphoryl carboxylate H3TBPPO ligand
have been constructed by solvothermal method and structurally characterized. Complexes 1, 2 and
3 are isostructural, all of them consist of trinuclear metal building units, and show a (4,
8)-connected 2-fold interpenetrating flu topological net, while complex 4 possesses a 3D 4-fold
interpenetrating dia network. The luminescent properties of complexes 1, 2, 4 and the magnetic
property of complex 3 have been investigated. Remarkably, the luminescent quantum yield of
complexes 1, 2 and 4 is up to 53.31%, 49.02% and 57.31%, respectively.