Syntheses and characterization of novel lanthanide adamantine-dicarboxylate coordination complexes

Article abstract of DOI:10.1016/j.jssc.2008.09.018

Hydrothermal reactions of 1,10-phenanthroline (phen), 1,3-adamantanedicarboxylic acid (H₂L) and lanthanide chlorides yielded six compounds: [Ln(L)(HL)(phen)] (Ln=Pr, 1; Nd, 2), [Ln(L)(HL)(phen)(H₂O)] (Sm, 3; Eu, 4), [Tb(L)(HL)(phen)(

Full text of DOI:10.1016/j.jssc.2008.09.018

ARTICLE IN PRESS
Journal of Solid State Chemistry 182 (2009) 95–101
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Syntheses and characterization of novel lanthanide adamantine–dicarboxylate
coordination complexes
Ã
Xing Li, Dan-Yi Wei, Shi-Jie Huang, Yue-Qing Zheng
Institute of Solid Materials Chemistry, State Key Laboratory Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering,
Ningbo University, Ningbo, Zhejiang 315211, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Hydrothermal reactions of 1,10-phenanthroline (phen), 1,3-adamantanedicarboxylic acid (H L) and
2
Received 12 June 2008
Received in revised form
lanthanide chlorides yielded six compounds: [Ln(L)(HL)(phen)] (Ln ¼ Pr, 1; Nd, 2), [Ln(L)(HL)(phen)
(H
2
O)] (Sm, 3; Eu, 4), [Tb(L)(HL)(phen)(H
2
O)]
2
ꢀ 2H
2 3 4 2
O (5), [Er (L) (OH)(phen)] (6). Compounds 1–4 are
7
September 2008
structurally featured by one-dimensional polymeric chains; 5 hold binuclear structure constructed from
eight-coordinated lanthanide center LnN of distorted bicapped trigonal prism bridged by
dicarboxylate ligands; 6 shows that erbium ions are in mono and bicapped trigonal prismatic
geometries, respectively, which are further connected by -OH to give rise to trinuclear structure.
Accepted 22 September 2008
Available online 9 October 2008
2 6
O
Keywords:
m
3
Adamantanedicarboxylate
Hydrothermal reaction
Lanthanide complexes
Thermogravimetric analyses of 1, 3 and 5 were performed. Fluorescent measurements of 4 and 5 were
carried out, respectively.
&
2008 Published by Elsevier Inc.
1
.
Introduction
adamantanedicarboxylic acid possesses intriguing coordination
behaviors and potential hydrogen-bond interactions, such as
asymmetric geometry and multiple coordination sites. However,
former studies on the coordination chemistry of 1,3-adamanta-
nedicarboxylic acid are mainly focused on transition metals
[36–38], and those on lanthanide matals were very limited [39].
Recently we began to use adamantanedicarboxylic acid as organic
ligand to synthesize lanthanide complexes, aiming at studying the
coordination chemistry of lanthanide adamantanedicarboxylic
acid as well as at obtaining some novel structures. By means of
hydrothermal technique, six new lanthanide complexes have
successfully prepared with 1,3-adamantanedicarboxylic acid. This
paper will report about the syntheses and characterizations of a
series of lanthanide adamantine–dicarboxylate complexes,
Design and syntheses of lanthanide complexes are of great
interest due to their various topological networks and crystal
packing motifs as well as potential applications in fluorescent
probes, magnetic materials, catalysts, molecular sensors [1–13]. In
virtue of the large radii and high coordination number of
lanthanide metals, the assembly of lanthanide complexes may
encounter many difficulties and great challenges in terms of
controlling their shapes and dimensions. However, the fascinating
structures and special properties of lanthanide complexes have
attracted increasing attention of scientists, and extensive inves-
tigation has been reported in the recent years [14–26].
It has been documented that the geometries and properties of
organic ligands exert great effect on structural frameworks of
lanthanide complexes, thus much effort has been devoted to
modify the building blocks and to control the assembled motifs
for desired products through the selection of different organic
ligands. Previous studies have shown that rigid bridging ligands
containing multicarboxylate groups are versatile ones for con-
structions of the robust networks or other porous coordination
polymers [27–35]. As known, lanthanide ions have high affinity
for hard donor atoms, and ligands with oxygen or hybrid
oxygen–nitrogen atoms, especially multicarboxylate ligands are
usually employed in construction for lanthanide complexes. 1,3-
[Ln(L)(HL)(phen)] (Ln ¼ Pr, 1; Nd, 2), [Ln(L)(HL)(phen)(H
(Sm, 3; Eu, 4), [Tb(L)(HL)(phen)(H O)] O (5), [Er (L) (OH)
ꢀ 2H
(phen)] (6).
2
O)]
2
2
2
3
4
2
2. Experimental section
2.1. Materials and methods
Except LnCl ꢀ nH O, which was prepared in our laboratory,
3
2
all chemicals of reagent grade were commercially available
and used without further purification. Elemental analyses(C, H
and N) were performed using a Perkin-Elmer 2400 CHNS/O
analyzer. The infrared spectrum of KBr pellets in the range 4000–
Ã
Corresponding author. Fax: +8657487600734.
ꢁ
1
E-mail address: zhengyueqing@nbu.edu.cn (Y.-Q. Zheng).
400 cm was recorded on a Shimadzu FTIR-8900 spectrometer.
0
022-4596/$ - see front matter & 2008 Published by Elsevier Inc.
doi:10.1016/j.jssc.2008.09.018

ARTICLE IN PRESS
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6
X. Li et al. / Journal of Solid State Chemistry 182 (2009) 95–101
Thermogravimetric measurements were carried out from
room temperature to 1000 1C for 1, to 800 1C for 3 and 5 on
preweighed samples in nitrogen stream using a Seiko Exstar6000
TG/DTA6300 apparatus with a heating rate of 10 1C/min. All the
excitation and emission spectra were measured with an Aminco
Bowman Series 2 instrument with a xenon arc lamp as the
excitation light source for the solid-state samples at room
temperature.
Anal. Cacd (%) for C36
N 3.41. Found (%): C 52.78, H 5.13, N 3.36. IR (
3410ms, 3059vw, 2902s, 2849s, 1684vs, 1612vs, 1522vs, 1418vs,
847s, 729s.
41 2
H N O10Tb (820.65): C 52.69, H 5.04,
ꢁ
1
n
cm ):
2.2.6. Synthesis of [Er
3 4
(L) (OH)(phen)]2 (6)
Pale red crystals were prepared similarly to 5 except using
Er
2
O
3
instead of
Y
2
O
3
(Yield 15%). Anal. Cacd (%) for
C
4
120
H
130
N
4
O
34Er
6
(3175.92): C 45.38, H 4.13, N 1.76; Found: C
2
2
.2. Preparation of complexes
-
1
5.51, H 4.06, N 1.79; IR (n cm ): 3410ms, 3059vw, 2902s, 2849s,
1684vs, 1612vs, 1522vs, 1418vs, 847s, 731s.
.2.1. Synthesis of [Pr(L)(HL)(phen)] (1)
Pale green powder of PrCl
evaporation of a solution of Pr
water boiling condition. A mixture of 1,3-adamantanedicarboxylic
acid (H L, 0.30 mmol, 0.0673 g), the above-prepared PrCl
ꢀ nH
0.106 g) and 1,10-phenanthroline (phen, 0.30 mmol, 0.0595 g) in
water (10 mL) was stirred for 1.0 h, and then sealed in a 23 mL
Teflon-lined stainless autoclave, which was heated at 170 1C for six
days and thereafter cooled slowly at 10 1C/h to room temperature,
and pale green crystals were seperated by filtering and washing
3
ꢀ nH
2
O was obtained by slow
2 3
O dissolved in HCl (10 mL) under
2
.3. X-ray crystallography
2
3
2
O
Suitable crystals of 1–6 were selected under a polarizing
(
microscope and fixed with epoxy cement on respective fine glass
fibers which were then mounted on a RIGAKU RAXIS-RAPID
diffractometer with graphite monochromated Mo K
a radiation
˚
(l
¼ 0.71073 A) for cell determination and subsequent data
collection for in the range of 3.22p
tion corrections were applied using the SADABS program. SHELXS-
7 and SHELXL-97 programs were used for structure solution and
yp27.481. Empirical absorp-
with absolute ethanol (Yield 40%, based on Pr
for C36 Pr (766.61): C 56.40, H 4.86, N 3.65. Found (%): C
6.85, H 4.97, N 3.59. IR(
684vs, 1608vs, 1518vs, 1408vs, 847s, 731s.
2 3
O ). Anal. Cacd (%)
37 2 8
H N O
9
ꢁ1
5
1
n cm ): 3396ms, 3055vw, 2903s, 2849s,
refinement [40,41]. The structures were solved by using direct
methods and followed by successive Fourier and difference
Fourier syntheses. All non-hydrogen atoms were refined with
anisotropic displacement parameters by full-matrix least-squares
technique and all hydrogen atoms with isotropic displacement
parameters. Detailed information about the crystal data and
structure determination is summarized in Table 1. Selected
interatomic distances and bond angles are given in Tables 2–7
(See in Supporting Materials). Crystallographic data (excluding
structure factors) for complexes 1–6 in this paper have been
deposited with Cambridge Crystallographic Data Centre as
supplementary publications.
2.2.2. Synthesis of [Nd(L)(HL)(phen)] (2)
Pale red crystal were prepared analogously to 1 except
using Nd
2
O
3
instead of Pr
2 3
O (Yield 35%). Anal. Cacd (%) for
C H N O Nd (769.94): C 56.16, H 4.84, N 3.64. Found (%):
36 37 2 8
ꢁ
1
C56.19, H 4.71, N 3.58. IR (
n cm ): 3422ms, 3080vw, 2883s,
2
847s, 1697vs, 1589vs, 1518vs, 1408vs, 851s, 731s.
2
.2.3. Synthesis of [Sm(L)(HL)(phen)(H
Yellow powder of SmCl O was obtained by slow evapora-
ꢀ nH
tion of a solution of Sm (0.150 mmol, 0.0525 g) dissolved in HCl
10 mL) under water boiling condition. A mixture of 1,3-adaman-
tanedicarboxylic acid (0.30 mmol, 0.0673 g), the above-prepared
SmCl O and 1,10-phenanthroline (0.30 mmol, 0.0595 g) in
2
O)] (3)
3
2
2 3
O
(
3
. Results and discussion
3
ꢀ nH
2
water (10 mL) was stirred for 30 min, and then sealed in a 23 mL
Teflon-lined stainless autoclave, which was heated at 160 1C for
three days and thereafter cooled slowly to room temperature, and
pale yellow crystals were seperated by filtering and washing
3
.1. Syntheses of the complexes
Owing the hydrophobility of the adamantane framework, 1,3-
adamantanedicarboxylic acid was found to be uneasily dissolved
in common solvents such as H O, MeOH, EtOH, THF, etc. under
2 3 39 2 9
(Yield 30%, based on Sm O ). Anal. Cacd (%) for C36H N O Sm
2
(
3
794.07): C 54.45, H 4.95, N 3.53. Found (%): C 55.01, H 4.81, N
.64. IR(n cm ): 3402ms, 3080w, 2902s, 1685vs, 1610vs, 1514vs,
ambient condition, therefore, the reactions of the dicarboxylatic
acid with lanthanide chlorides were carried out under the similar
hydrothermal conditions in order to obtain new complexes
with novel networks. Six lanthanide metal-organic complexes
suitable for single crystal X-ray diffraction were obtained. 1,3-
adamantanedicarboxylates function as linkers in various fashions
ꢁ1
1408vs, 848s, 729s.
2
.2.4. Synthesis of [Eu(L)(HL)(phen)(H
Colorless crystals were prepared analogously to 3 except
using Eu instead of Sm (Yield 45%). Anal. Cacd (%) for
Eu (796.67): C 54.34, H 4.94, N 3.52. Found (%):
2
O)] (4)
2
O
3
2 3
O
(
monodentate, bidente bridging, bidentate chelate, bidente che-
36 39 2 9
C H N O
lating–bridging etc.) through its carboxylate groups in these
complexes (Scheme 1), demonstrating its versatility in construc-
tion of the robust network or porous functional materials [36–39].
The structural analyses show that Ln(III) ions are the nine-
coordinated modes in 1 and 2, the eight-coordinated modes in 3, 4
and 5, the 8/7-coordinated fashions in 6, respectively. On the
other hand, complexes 1, 2, 3 and 4 possess one-dimensional
chain frameworks, however, complex 5 is binuclear structure, and
complex 6 has double chains extended by two inequivalved
structural units. The different geometries and structures may
result from the effects of the lanthanide contraction on crystal
structural formation, which would offer a helpful route to design
and synthesize lanthanide compounds with the special structural
networks.
ꢁ
1
C54.57, H 4.82, N 3.48. IR (
n cm ): 3410ms, 3059vw, 2902s,
2
849s, 1684vs, 1612vs, 1522vs, 1418vs, 847s, 730s.
2
.2.5. Synthesis of [Tb(L)(HL)(phen)(H
Pale green powder of TbCl
ꢀ nH
evaporation of a solution of Tb (0.07 mmol, 0.0549 g) dissolved
in HCl (5 mL) under water boiling condition. A mixture of 1,3-
adamantanedicarboxylate (0.30 mmol, 0.0672 g), TbCl
2
O)]
2 2
?2H O (5)
3
2
O was obtained by slow
4 7
O
3
ꢀ nH
2
O
nd 1,10-phenanthroline (0.30 mmol, 0.0595 g) in water (10 mL)
was stirred for 30 min, and sealed in a 23 mL Teflon-lined stainless
autoclave, which was heated at 170 1C for three days and
thereafter cooled slowly to room temperature, and Pale green
crystals were seperated by filtering and washing (Yield 30%).

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X. Li et al. / Journal of Solid State Chemistry 182 (2009) 95–101
97
Table 1
Crystallographic data for 1–6
1
2
3
4
5
6
Empirical formula
C
36
H
37 2
N O
8
Pr
C
36
H
2
37NdN O
8
C
36
H
N
39 2
O
9
Sm
C
36
H39EuN
2
O
9
C
36
H
N
41 2
O
10Tb
C
120 6 4 34
H130Er N O
Formula mass
766.59
769.92
Triclinic
P1¯
794.04
Triclinic
P1¯
795.65
Triclinic
P1¯
820.63
Triclinic
P1¯
3175.84
Triclinic
P1¯
Crystal system
Triclinic
Space group
P1¯
a
b
c
11.167(2)
11.141(2)
12.403(3)
13.302(3)
109.36(3)
98.57(3)
110.20(3)
1553.7(5)
2
11.153(2)
11.133(2)
12.312(3)
12.681(3)
109.13(3)
97.31(3)
99.72(3)
1587.2(5)
2
8.636(2)
12.805(3)
18.094(4)
26.128(5)
80.69(3)
86.39(3)
84.09(3)
5936.2(2)
2
12.407(3)
13.292(3)
109.38(3)
98.54(3)
110.16(3)
1557.4(5)
2
12.329(3)
12.651(3)
109.04(3)
97.19(3)
99.83(3)
1589.5(5)
2
13.573(3)
14.579(3)
94.59(3)
96.33(3)
92.30(3)
1691.0(6)
2
a
b
g
(deg)
(deg)
(deg)
V (A˚
3
)
Z
3
r
m
(Mg/m )
1.635
1.646
1.659
1.665
1.612
1.777
-
1
(mm
)
1.623
1.730
1.909
2.038
2.513
4.274
F (000)
range (deg)
780
782
806
808
832
3116
y
3.02–27.48
15337
7068
3.02–27.48
15251
3.04–27.48
15768
7237
3.04–27.48
15453
7168
3.02–27.48
16764
3.04–27.48
54559
25969
18087
Reflns collected
Reflns independent
Reflns observed
7009
7671
6789
6423
6872
6663
6824
R1 [IX2
R1 (all data)
GOF
s
(I)]
0.0188
0.0202
1.190
0.0427
0.0468
1.095
0.0300
0.0318
1.192
0.0320
0.0357
1.161
0.0276
0.0344
1.074
0.0611
0.0940
1.002
2
o
2
c
2
2 2 1/2
) ]
(a) wR
2
¼ [S
w(F
–F
) /
S
w(F
o
.
Scheme 1. Linking fashions of the adamantanedicarboxylate groups.
˚ ˚
2.700 A (average 2.687 A). For adamantane–dicarboxylate ligand
3
.2. Description of the crystal structures
2
ꢁ
of each structural unit, L acts as a
3
m -bridge to link three Pr(III)
X-ray diffraction studies reveal that the asymmetric unit of
ion with one carboxylate group adopting a bidentate chelate mode
coordinating to one praseodymium ion and the other adopting a
bidente chelating–bridging mode connecting two praseodymium
complex 1 contains one Pr(III) ion, one phen ligand and two kinds
of coordiantion styles of 1,3-adamantanedicarboxylate ligand
1
ꢁ
2ꢁ
1ꢁ
(HL , L ). As shown in Fig. 1a, the nine-coordinated Pr(III) ion
ion (Scheme 1b) [42,43]; HL , the monoprotonated adamanta-
is in a tricapped trigonal antiprism LnN defined by seven
oxygen atoms of the different 1,3-adamantanedicarboxylate and
two N atoms of one phen ligand with Pr–O distances ranging from
2
O
7
nedicarboxylate, links two praseodymium ions through the
carboxylate group acting as a bidentate bridge mode and the
protonated end remains uncoordinated (Scheme 1f). Two adjacent
praseodymium ions are held together to form a dimeric subunit
˚ ˚
.408 to 2.742 A (average 2.512 A), Pr–N distances of 2.674 and
2

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X. Li et al. / Journal of Solid State Chemistry 182 (2009) 95–101
Fig. 1. (a) ORTEP view of coordination environments of Ln(III) ion with 30% displacement ellipsoids and (b) two dimensional layer structure projected along b axis in 1 and
2.
Fig. 2. (a) ORTEP view of coordination environments of Ln(III) ion with 30% displacement ellipsoids and (b) a fragment of a double chain along c axis in 3 and 4.
[
2 2 2 2
Pr (L) (HL) (phen) ] by the carboxylates with Pr–Pr distance
˚
of 3.96 A, implying no significant direct interaction between
metal ions.
[
2 2 2 2
Pr (L) (HL) (phen) ] can be viewed as the basic building block
for the whole structure of 1. Each pair of such blocks are bridged
by adamantanedicarboxylate bridging, giving rise to a double
chain. The chains are further connected through strong offset
face-to-face
pꢀ ꢀ ꢀ p stacking interaction with a mean interplanar
˚
distance of 3.25 A between the adjacent aromatic rings to
generate two-dimensional network (Fig. 1b). Complex 1 finally
forms three-dimensional packing structure by hydrogen bond
˚
of the carboxylate oxygen atoms with O ꢀ ꢀ ꢀ O distance 2.658 A and
+
(O–H ꢀ ꢀ ꢀ O) ¼ 1611, as well as weak C–H ꢀ ꢀ ꢀ O and C–H ꢀ ꢀ ꢀ N
˚
interactions with C ꢀ ꢀ ꢀ O ¼ 3.385 A and +(C–H ꢀ ꢀ ꢀ O) ¼
˚
1
491; C ꢀ ꢀ ꢀ N ¼ 3.349 A, and +(C–H ꢀ ꢀ ꢀ N) ¼ 1551, respectively
(
Fig. S10).
Complex 2, being isomorphous to 1, possesses one-dimen-
sional network by covalent bonding. The Nd–O distances fall in a
˚
˚
range from 2.393–2.742 A (average 2.509 A), and Nd–N from 2.660
˚
˚
to 2.685 A (average 2.673 A), which slightly shorter than oens in 1,
resulting from the effect of lanthanide contraction.
Complexes 3 and 4 are allomers with one-dimensional chain
structure by covalent bonding. Two kinds of coordination modes
Fig. 3. Two-dimensional network through hydrogen bonds in 3 and 4.
1
ꢁ
2ꢁ
of adamantanedicarboxylate (HL
,
L
)
are present in the
2
ꢁ
structre: L acts as
m
3
-bridge to link three Ln(III) ion, in which
distorted bicapped trigonal prism LnN
2
O
6
with the metal to
˚
one carboxylate group adopts a bidentate chelate mode coordi-
nating to one lanthanide ion while the other adopts a bidente
bridging mode connecting two lanthanide ion (Scheme 1c)
ligating atom distances Sm–O ¼ 2.297–2.512 A, Sm–N ¼ 2.633–
˚
˚
˚
2.659 A in 3; Eu–O ¼ 2.2291–2.499 A, Eu–N ¼ 2.620–2.643 A in 4.
[Ln (L) (phen) ], being as dimeric subunits, are formed by
2
2
2
1
ꢁ
[
42–45]; and HL , the protonated adamantanedicarboxylate,
carboxylate linkers, which are reproduced through adamantane-
dicarboxylate bridging, giving rise to a double chain structure
(Fig. 2b). The chains are further extended into two-dimensional
network through hydrogen bonds between the carboxylate
links only one lanthanide ion through the carboxylate group
acting as a monodentate mode while the protonated one remains
uncoordinated to metal ion (Scheme 1e). As shown in Fig. 2a, the
Sm(III) or Eu(III) ion is in a eight-coordinated geometry defined by
˚
and aqua oxygen atoms with distance O–H ꢀ ꢀ ꢀ O ¼ 2.647–2.878 A
2
ꢁ
1ꢁ
four oxygen atoms from L , one oxygen from the HL , one aqua
oxygen atom and two nitrogen atoms from phen ligand, forming a
and +(O–H ꢀ ꢀ ꢀ O) ¼ 1501, as well as weak C–H ꢀ ꢀ ꢀ O interaction
˚
with C–H ꢀ ꢀ ꢀ O ¼ 3.352 A and +(C–H ꢀ ꢀ ꢀ O) ¼ 1471 in 3;

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99
˚
O–H ꢀ ꢀ ꢀ O ¼ 2.643–2.873 A, +(O–H ꢀ ꢀ ꢀ O) ¼ 149 ¼ 1781, C–H ꢀ ꢀ ꢀ
structure: (a) the adamantane–dicarboxylate acts as
m
3
-bridge
˚
O ¼ 3.339 A and +(C–H ꢀ ꢀ ꢀ O) ¼ 1471 in 4, respectively (Fig. 3).
to link three erbium ions, in which one carboxylate adopts a
chelate mode coordinating to one erbium ion while the other
adopts a bridging mode connecting two erbium ions (Scheme 1c);
Complex 5 possesses binuclear structural motifs constructed
by Tb(III) ions, phen, water molecule and adamantanedicarbox-
ylate (HL , L ). As shown in Fig. 4, the Tb(III) ion is in a eight-
coordinated fashion by four oxygen atoms from L , one oxygen
from HL , one oxygen from a coordination water and two
1
ꢁ
2ꢁ
(b) acts as
4
m -bridge to link four erbium ions, in which one
2
ꢁ
carboxylate adopts a bridging mode coordinating to two erbium
ions while the other adopts a chelate bridging mode connecting
1
ꢁ
nitrogen atoms from a phen ligand, forming a distorted bicapped
˚
two erbium ions (Scheme 1d). The OH-group acts as
linking three erbium ions (Scheme 1h) with distances
3
m -bridge
trigonal prism TbN
2
O
6
with distances Tb–O ¼ 2.248–2.445 A,
˚
˚
˚
Tb–N ¼ 2.525–2.577 A. The adamantanedicarboxylate ligands dis-
Er–O ¼ 2.268, 2.349, 2.354 A, Er–Er ¼ 3.776–4.160 A in the unit
2
ꢁ
˚
˚
play two types of linking modes in the structures: L acts as a
m
2
-
A; Er–O ¼ 2.254, 2.345, 2.349 A, Er–Er ¼ 3.725–4.135 A in the
unit B, indicating no substantial interaction among erbium
ions. The asymmetry units A and B grow into one-dimensional
chains by covalent bonding, respectively, and are finally extended
into three-dimensional supramolecular network by Van der
Waals forces and weak C–H ꢀ ꢀ ꢀ O interacion with distances
bridge to connect two Tb(III) ions with each carboxylate chelating
1
ꢁ
one lanthanide ion (Scheme 1a); HL , the protonated adamanta-
nedicarboxylate, links a lanthanide ion by the deprotonated
carboxylate group acting as a monodentate mode while the
protonated end remains uncoordinated (Scheme 1e). Different
kinds of hydrogen bondings are observed in 5: (a) hydrogen
bondings between uncoordinated water molecule/coordinated
˚
C ꢀ ꢀ ꢀ O ¼ 3.34–3.42 A (Fig. S11).
˚
water molecule (O ꢀ ꢀ ꢀ O distances: 2.552 A); (b) uncoordinated
water molecule/carboxylate oxygen atoms (O ꢀ ꢀ ꢀ O distances:
˚
2
.665, 2.698 A); (c) coordinated water molecules/carboxylate
˚
oxygen atoms (O ꢀ ꢀ ꢀ O distance: 2.743 A); The presence of the
extensive hydrogen bonding interaction results in formation of
one-dimensional chains, which further grow into two-dimen-
sional layer-like network by offset face-to-face
pꢀ ꢀ ꢀ p stacking
˚
interaction with a mean interplanar distance of 3.383 A between
adjacent phen ligands belonging to neighboring chains (Fig. 5).
Compound 6 contains two types of crystallographic distinct
units (A and B), each of which is composed of three Er(III) ions,
one OH, one phen and four adamantanedicarboxylate ligands
(
Fig. 6). In asymmetry unit A, Er(III) ions have different coordina-
tion environments: Er1 and Er2 are eight-coordinated dodecahe-
dron ErO
8
by one hydroxy oxygen atom, and seven carboxylate
˚
oxygen atoms with distances Er–O ¼ 2.208–2.759 A; Er3 is in
seven-coordinated mode by two nitrogen atoms of phen, one
hydroxy oxygen atom, four oxygen atoms of different adamanta-
nedicarboxylates, forming capped octahedron with distances
˚
˚
ErꢁO ¼ 2.190–2.346 A, Er–N ¼ 2.494 and 2.531 A, respectively;
three Er(III) ions grow into an interesting trimeric unit Er
3 2 17
N O
through sharing a common vertex of the polyhedra. In asymmetry
unit B, Er4, Er6 and Er5 are similar to Er1, Er2 and Er3 in terms
of cooridination modes. The adamantanedicarboxylate ligands
exhibit two types of linking modes to bridge erbium ions in the
Fig. 5. Two-dimensional framework in 5.
Fig. 4. ORTEP view of coordination environments of Tb(III) ion with 50% displacement ellipsoids for 5.

ARTICLE IN PRESS
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X. Li et al. / Journal of Solid State Chemistry 182 (2009) 95–101
3.3. Thermogravimetric analysis (TGA)
TGAs for complexes 1, 3 and 5, have been measured under a
flow of nitrogen gas. The DTA curves of complex 1 display two
endothermic peaks at 150 and 222 1C, respectively, which
indicated that the complex undergo the chemical reactions or
physical process at corresponding temperature. The first weight
loss of 23.0% (calcd: 23.4%) over 150–298 1C corresponds well to
the loss of one phen per formula unit [Pr(L)(HL)(phen)]. Upon
further heating, one endothermic peak was observed at 570 1C
with the final residue of 22.4% at 979 1C, presumably being Pr
2 3
O
(calcd: 21.5%). For 3, DTA studies show four endothermic peaks at
192, 330, 470 and 581 1C, respectively. The first weight loss of
2
.14% (calcd: 2.26%) over 179–224 1C could be contributed to the
)(C12 )(phen)(H O)]. The second
dehydration of [Sm(C12
H
14
O
4
H
15
O
4
2
weight loss of 39.8% (calcd: 40.1%) from 310 to 345 1C results from
ꢁ
release of one C12
H
15
O
4
ligand and 0.5 molecular phen per
molecular unit. The final decomposition product, is presumably
Sm , 19.8% (calcd: 20.7%) heating upon to 720 1C. For 5, DTA
2 3
O
studies show four endothermic peaks at 120, 200, 319 and 490 1C,
respectively. The first weight loss of 4.35% (calcd: 4.39%) from 60
to 228 1C is due to the loss of two water per formula unit
Fig. 7. The solid-state luminescent spectrum for 4.
[
(
Tb(L)(HL)(phen)(H
calcd: 22.2%) from 260 to 364 1C corresponds to the loss of one
2
O)]
2
ꢀ 2H
2
O; the second weight loss of 25.5%
phen per formula unit. The final decomposition product is
assumed to be Tb , 20.0% (calcd: 21.9%).
3 4
O
3.4. Fluorescence properties
Complex 4 in solid-state displays three fluorescent emission
peaks at 580 (weak), 592 (mediate) and 614 nm (strong) upon
photoexcitation at 341 nm, respectively (Fig. 7). The photolumi-
nescence emission may be assigned to the excitated radiative
5
7
decay of europium ions: 614 nm attributed to
0 2
D - F , 592 nm
5
7
5
7
0 1 0 0
attributed to D - F , and 580 nm attributed to D - F energy
transitions by 4f–4f orbits [46–49], which are consistent with the
known characteristic peaks of europium ions, indicating that the
effect of the photoluminescence of organic ligands could be
negligible in compound 4.
As shown in Fig. 8, compound 5 presents four fluorescent
5
7
5
7
emission peaks: 491 nm ( D
4
- F
6 4 5
, strong), 545 nm ( D - F ,
5
7
5
7
very strong), 585 nm ( D
4
- F
4
, weak) and 623 nm ( D
4
- F
3
, very
Fig. 8. The solid-state luminescent spectrum for 5.
Fig. 6. Local coordination environment of erbium ions with 30% displacement ellipsoids in 6.

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X. Li et al. / Journal of Solid State Chemistry 182 (2009) 95–101
101
weak), respectively, in the solid state upon photoexcitation at
47 nm. The strong luminescence emission at 545 nm may result
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from supersensitive effect of the terbium ion. The peak positions
of fluorescent emission of the Tb-compound are consistent with
the known ones for free terbium ions, indicating that the effect of
the photoluminescence of organic ligands could be negligible in
compound 5.
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In summary, six new lanthanide metal-organic frameworks
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13] F.F. Chen, Z.Q. Bian, Z.W. Liu, D.B. Nie, Z.Q. Chen, C.H. Huang, Inorg. Chem. 47
have been synthesized by hydrothermal reactions, and the
complexes exhibit the different frameworks. The diverse struc-
tures imply subtle effects of lanthanide ion radii on crystal
structural formation. Complex 5 illustrates remarkable thermal
stability and strong photoluminescent emission at the solid state.
The contribution may afford useful information for the construc-
tion of lanthanide photoluminescent materials.
(
2008) 2507.
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Acknowledgment
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The project was supported by the the Expert Project of Key
Basic Research of the Ministry of Science and Technology of China
grant No. (2003CCA00800) Science and Technology Department of
Zhejiang Province (grant No. 2006C21105), Education Department
of Zhejiang Province, and the Ningbo Municipal Natural Science
Foundation grant No. (2006A610061). The thanks are also
extended to K.C. Wong Magna Fund in Ningbo University.
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X-ray crystallographic files for compounds 1–6 in CIF format, IR
spectra for 1–6, TGA spectra for 1, 3 and 5. CCDC number 683833-
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6
83838 for 1–6 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cam-
bridge Crystallographic Data Centre, 12, Union Road, Cambridge
CB2 1EZ, UK; fax: (internat.) +441223/336 033; E-mail: depos-
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Appendix B. Supplementary material
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Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.jssc.2008.09.018.
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