Syntheses, crystal structures, and characterizations of a series of new layered lanthanide carboxylate-phosphonates

Article abstract of DOI:10.1002/ejic.200600039

Hydrothermal reactions of different lanthanide(III) salts with (H ₂O₃PCH₂)₂NCH₂COOH (H ₅L¹) led to two new layered lanthanide(III) carboxylate-diphosphonates, namely La(H₂L¹)(H ₂O)₂·H₂O (1) and La(H₂L ¹)(H₂O) (2). The structure of compound 1 features a layered architecture in which the nine-coordinate La³⁺ ions are bridged by phosphonate groups of the ligands. The carboxylate group of the phosphonate ligand remains protonated and is involved in the interlayer hydrogen bonding. Compound 2 features a double layer structure in which the La ³⁺ ion is eight-coordinated and the carboxylate group of the ligand is chelated to a La³⁺ ion in a bidentate fashion. Hydrothermal reactions of lanthanide(III) salts with 4-HOOC-C₆H ₄-CH₂N(CH₂PO₃H₂) ₂ (H₅L²) afforded three new compounds, namely, La(H₄L²)(H₃L²)(H₂O) ·2H₂O (3), Er(H₃L²)(H₄L ²) (4), and Er(HL³)(H₂L³)(H ₂O) (5) [H₂L³ = H₂O ₃PCH₂N(CHO)(CH₂-C₆H ₄-COOH)]. H₂L³ was formed by the in situ oxidation of one P-C bond of the H₅L² ligand. Compound 3 features a (002) lanthanum(III) phosphonate layer in which the seven-coordinate La³⁺ ions are bridged by diphosphonate moieties of the ligands. The carboxylate group remains protonated and is involved in the interlayer hydrogen bonding. The structure of compound 4 contains a 1D chain along the a axis in which each pair of ErO₆ octahedra is bridged by a pair of phosphonate groups. These 1D chains are further interconnected by hydrogen bonds between noncoordinated phosphonate oxygen atoms into a (002) layer with the phenyl carboxylate groups hanging on the interlayer space. The structure of compound 5 is also layered. The interconnection of Er³⁺ ions by bidentate and tetradentate bridging phosphonate groups resulted in a (002) inorganic layer with the organic groups orientated to the interlayer space. Luminescence properties of compounds 4 and 5 have also been studied. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

Full text of DOI:10.1002/ejic.200600039

FULL PAPER
DOI: 10.1002/ejic.200600039
Syntheses, Crystal Structures, and Characterizations of a Series of New
Layered Lanthanide Carboxylate-Phosphonates
Si-Fu Tang,[a] Jun-Ling Song,[a] and Jiang-Gao Mao*[a]
Keywords: Lanthanides / Phosphonate / Luminescence
Hydrothermal reactions of different lanthanide(III) salts with
(H2O3PCH2)2NCH2COOH (H5L1) led to two new layered
phosphonate layer in which the seven-coordinate La3+ ions
are bridged by diphosphonate moieties of the ligands. The
carboxylate group remains protonated and is involved in the
interlayer hydrogen bonding. The structure of compound 4
contains a 1D chain along the a axis in which each pair of
ErO6 octahedra is bridged by a pair of phosphonate groups.
These 1D chains are further interconnected by hydrogen
bonds between noncoordinated phosphonate oxygen atoms
into a (002) layer with the phenyl carboxylate groups hang-
ing on the interlayer space. The structure of compound 5 is
also layered. The interconnection of Er3+ ions by bidentate
and tetradentate bridging phosphonate groups resulted in a
(002) inorganic layer with the organic groups orientated to
the interlayer space. Luminescence properties of compounds
4 and 5 have also been studied.
lanthanide(III
)
carboxylate-diphosphonates, namely La-
(H2L1)(H2O)2·H2O (1) and La(H2L1)(H2O) (2). The structure of
compound 1 features a layered architecture in which the
nine-coordinate La3+ ions are bridged by phosphonate
groups of the ligands. The carboxylate group of the phos-
phonate ligand remains protonated and is involved in the
interlayer hydrogen bonding. Compound 2 features a double
layer structure in which the La3+ ion is eight-coordinated and
the carboxylate group of the ligand is chelated to a La3+ ion
in a bidentate fashion. Hydrothermal reactions of lantha-
nide(III) salts with 4-HOOC–C6H4–CH2N(CH2PO3H2)2 (H5L2)
afforded three new compounds, namely, La(H4L2)(H3L2)-
(H2O)·2H2O (3), Er(H3L2)(H4L2) (4), and Er(HL3)(H2L3)(H2O)
(5) [H2L3 = H2O3PCH2N(CHO)(CH2–C6H4–COOH)]. H2L3
was formed by the in situ oxidation of one P–C bond of the
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
H5L2 ligand. Compound 3 features a (002) lanthanum(III
)
big obstacles for the structural studies for these lantha-
nide() compounds. The elucidation of the structures of
lanthanide phosphonates is very important, as these com-
pounds may exhibit useful luminescent properties in both
visible and near IR regions.[12] A series of lanthanide di-
phosphonates with a 3D pillared-layer structure were iso-
lated by the Ferey group.[13] Several lanthanide phosphon-
ates with a crown ether or calixarene moiety have been re-
ported by Clearfield, Bligh, Lukes, and Lin et al.[8a,14] Their
structures normally feature a chelating mononuclear unit or
a layer architecture. A series of one-dimensional lanthanide
diphosphonates containing a hydroxy group were also re-
ported.[15] Results from our group indicate that introducing
a second ligand such as 5-sulfoisophthalic acid (H3BTS) or
oxalate acid, whose lanthanide compounds have good solu-
bility and very good crystallinity, into the lanthanide–phos-
phonate system can lead to novel luminescent lanthanide
phosphonate hybrids.[16] Another useful alternative method
is the use of a phosphonic acid to which the carboxylate
group or amino acid moiety is directly attached. So far, re-
search on this aspect is scarce. Only a few 2D or 3D lantha-
nide phosphonates with additional carboxylate group or
amino acid moiety have been prepared.[17] We have initiated
a research project to systematically study the influence of
counteranion, pH value, the ionic size of the lanthanide()
Introduction
During the past two decades, a lot of research attention
has been devoted to the chemistry of metal phosphonates
for their potential applications in the areas of catalysis, ion
exchange, proton conductivity, intercalation chemistry, pho-
tochemistry, and materials chemistry.[1] Most metal phos-
phonates exhibit a variety of open framework architectures
such as layered and microporous structures. The use of bi-
functional or multifunctional anionic units, such as diphos-
phonates, aminophosphonates, or phosphonocarboxylates,
has been found to be an effective method to prepare new
materials with microporous or open framework struc-
tures.[2–5] Results from ours and other groups indicate that
amino-carboxylic-phosphonic acids are good ligands for
building inorganic–organic hybrid open frameworks.[6] Re-
ports on lanthanide phosphonates are rather limited and a
number of them are based on X-ray powder diffrac-
tion.[7–11,13–16] Low solubility and poor crystallinity are two
[a] State Key Laboratory of Structural Chemistry, Fujian Institute
of Research on the Structure of Matter, Chinese Academy of
Sciences,
Fuzhou 350002, P. R. China
E-mail: mjg@ms.fjirsm.ac.cn
Supporting information for this article is available on the
WWW under http://www.eurjic.org or from the author.
Eur. J. Inorg. Chem. 2006, 2011–2019
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2011

S.-F. Tang, J.-L. Song, J.-G. Mao
FULL PAPER
ion and the substituent on the structures, and luminescence ions. Two phosphonate oxygen atoms [O(11) and O(12)] are
properties of lanthanide amino-carboxylate-phosphonates bidentate metal linkers. The carboxylate group of the ligand
formed. Two carboxylate-phosphonic acids, H5L1 [H5L1 = remains protonated and noncoordinated; so does its amine
(H2O3PCH2)2NCH2COOH] and H5L2 [H5L2 = 4-HOOC– group. The protonation of the amine group in a phos-
C6H4–CH2N(CH2PO3H2)2], in which the carboxylate group phonate ligand is well known, as amino-phosphonic acid
is well separated from the diphosphonate moiety were se- usually exists as a zwitterion in which a proton of the phos-
lected. Hydrothermal reactions of the lanthanide() salts phonate group is transferred to the basic amine group.[1,5]
with the above two phosphonic acids afforded five
new compounds, namely, La(H2L1)(H2O)2·H2O (1),
La(H2L1)(H2O) (2), La(H4L2)(H3L2)(H2O)·2H2O (3),
Er(H3L2)(H4L2) (4), and Er(HL3)(H2L3)(H2O) (5) [H3L3 =
H2O3PCH2N(CHO)(CH2–C6H4–COOH)]. H3L3 resulted
from the in situ oxidation of one P–C bond of the H5L2
ligand during the reaction (Scheme 1). Herein we report
their syntheses, crystal structures, and luminescent proper-
ties.
Figure 1. ORTEP representation of the selected unit of compound
1. The thermal ellipsoids are drawn at 50% probability. The lattice
Scheme 1. The formation of H3L3 by the in situ oxidation of H5L2.
water molecules have been omitted for clarity. Symmetry codes for
generated atoms: A) x, –y + 1/2, –z – 1/2; B) –x + 2, –y + 1,
–z + 1; C) x, –y + 3/2, –z – 1/2; D) –x + 2, –y – 1/2, –z + 3/2;
E) –x + 2, y + 1/2, –z + 3/2; F) x, –y + 1/2, z + 1/2; G) x, –y +
3/2, z + 1/2.
Results and Discussion
The interconnection of the La3+ ions by bridging phos-
phonate ligands resulted in (100) inorganic layers with the
carboxylate moieties orientating toward the interlayer space
(Figure 2). The interlayer distance is about 12.0 Å. Neighb-
oring layers are held together by hydrogen bonds among
carboxylate oxygens, noncoordinated phosphonate oxygen
[O(10)], aqua ligand O(2w), and lattice water [O(3w)]
(Table 1).
Hydrothermal reactions of different lanthanide() salts
with (H2O3PCH2)2NCH2COOH (H5L1) at two different
temperatures lead to two new layered lanthanide() car-
boxylate-diphosphonates, namely La(H2L1)(H2O)2·H2O (1)
and La(H2L1)(H2O) (2). The higher temperature used for
the synthesis resulted in compound 2 with fewer water
molecules. Hydrothermal reactions of lanthanide() salts
with 4-HOOC–C6H4–CH2N(CH2PO3H2)2 (H5L2) afforded
three new compounds, namely, La(H4L2)(H3L2)(H2O)·
2H2O (3), Er(H3L2)(H4L2) (4), and Er(HL3)(H2L3)(H2O)
(5) [H2L3 = H2O3PCH2N(CHO)(CH2–C6H4–COOH)]. The
higher number of water molecules present in the lantha-
num() compound are probably due to the higher coordi-
nation number for the La3+ ion than that for the Er3+ ion.
H2L3 was formed by the in situ oxidation of one P–C bond
of the H5L2 ligand by oxidizing nitrate anion. Hence the
counteranion, the temperature, and the ionic size of the lan-
thanide() ion have a strong effect on lanthanide phos-
phonates formed.
Compound 1 features a layered structure. The LaIII ion
is nine-coordinate by seven phosphonate oxygen atoms
from five {H2L1}3– anions and two aqua ligands (Figure 1).
The La–O distances are in the range 2.4453(19)–2.888(2) Å,
which is comparable to those reported for other LaIII phos-
phonates.[16] The H2L1 anion is septadentate; it chelates bi-
dentately with one La3+ ion by using a phosphonate group
and another LaIII ion by using two oxygen atoms from two
Figure 2. View of the structure of compound 1 down the b axis.
The phosphonate tetrahedra are shaded in medium gray. La, C, N,
and O atoms are drawn as open, black, octand, and crossed circles,
phosphonate groups, and also bridges with three other LaIII respectively.
2012
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New Layered Lanthanide Carboxylate-Phosphonates
FULL PAPER
Compound 2 has a different layered structure. The asym- Table 1. (continued)
metric unit of 2 consists of one unique La3+ ion, one
Compound 5
2.213(6) P(2)–O(23)
{H2L1}3– anion, and an aqua ligand (Figure 3). The La3+
Er(1)–O(13)#1
ion is eight-coordinate by five phosphonate oxygen atoms
Er(1)–O(23)#2
1.523(6)
1.549(6)
2.239(7)
2.253(7)
2.290(6)
2.356(7)
2.403(6)
2.437(6)
1.497(6)
1.502(6)
1.586(8)
1.517(7)
2.585(13)
P(2)–O(21)
N(1)–C(4)
N(2)–C(21)
O(5)–C(4)
O(6)–C(21)
C(6)–O(1)
C(6)–O(2)
C(27)–O(4)
C(27)–O(3)
O(1)···O(4)#4
from five phosphonate groups of four {H2L1}3– anions, two
Er(1)–O(12)
1.314(13)
1.285(14)
1.167(14)
1.186(14)
1.266(16)
1.290(14)
1.228(16)
1.270(17)
2.614(13)
carboxylate oxygens of another phosphonate ligand, and an Er(1)–O(21)#3
Er(1)–O(1w)
aqua ligand. The La–O distances are in the range 2.360(9)–
Er(1)–O(21)
2.728(8) Å, which is comparable to those in compound 1
Er(1)–O(22)
and other lanthanum() phosphonates.[16] The coordinat-
P(1)–O(12)
ing mode of the phosphonate anion is different from that
P(1)–O(13)
P(1)–O(11)
P(2)–O(22)
O(2)···O(3)#4
Table 1. Selected bond lengths [Å] for compounds 1–5.[a]
Compound 1
[a] Symmetry transformations used to generate equivalent atoms:
For 1: #1 x, –y + 1/2, –z + 1/2; #2 –x + 2, –y + 1, –z + 1; #3 x, –
y + 3/2, –z – 1/2; #4 –x + 2, y – 1/2, –z + 3/2; #5 –x + 1, –y – 1/
2, –z + 3/2; #6 –x + 1, –y + 1, –z + 1; #7 x, 1/2 – y, 1/2 + z. For
2: #1 –x – 1/2, y, z – 1/2; #2 x + 1/2, –y, z; #3 x + 1, y, z; #4 –x –
1/2, y, z + 1/2; #5 –1/2 + x, –y, z. For 3: #1 –x + 2, –y + 1, –z +
1; #2 –x + 2, –y + 2, –z + 1; #3 –x + 1, –y + 1, –z + 1; #4 x, y, z
+ 1; #5 –x + 2, –y + 2, –z + 2; #6 –x + 2, –y + 1, –z; #7 –x + 1, –
y + 2, –z + 1; #8 x – 1, y, z. For 4: #1 –x + 1, –y + 2, –z + 1; #2 –
x + 2, –y + 2, –z + 1; #3 x + 1, y, z; #4 –x + 1, –y + 1, –z; #5 –x
+ 1, –y + 3, –z + 1; #6 –x, –y + 1, –z + 1. For 5: #1 –x, –y + 2, –
z + 1; #2 –x – 1, –y + 1, –z + 1; #3 –x, –y + 1, –z + 1; #4 x + 1,
y + 1, –1 + z.
La(1)–O(21)#1
La(1)–O(20)#2
La(1)–O(11)#1
La(1)–O(22)
La(1)–O(1w)
La(1)–O(12)#3
La(1)–O(2w)
La(1)–O(12)#4
La(1)–O(11)#4
O(1)···O(2 W)#7
2.445(2)
2.485(2)
2.509(2)
2.517(2)
2.564(2)
2.587(2)
2.589(3)
2.694(2)
2.888(2)
2.800(4)
P(1)–O(12)
P(1)–O(10)
P(2)–O(22)
P(2)–O(20)
P(2)–O(21)
C(4)–O(1)
C(4)–O(2)
O(2)···O(10)#5
O(2)···O(2w)#6 2.835(4)
O(10)···O(3 W)
1.524(2)
1.534(2)
1.520(2)
1.523(2)
1.524(2)
1.225(4)
1.276(4)
2.478(3)
2.822(4)
Compound 2
La(1)–O(11)#1
La(1)–O(22)#2
La(1)–O(21)#3
La(1)–O(12)#3
La(1)–O(23)#4
La(1)–O(1w)
La(1)–O(1)
2.360(9)
2.407(9)
2.456(8)
2.469(9)
2.509(9)
2.630(9)
2.693(8)
3.24(1)
La(1)–O(2)
P(1)–O(11)
P(1)–O(12)
P(1)–O(13)
P(2)–O(21)
P(2)–O(22)
P(2)–O(23)
2.728(8)
1.499(9)
1.504(8)
1.562(8)
1.489(9)
1.508(9)
1.515(9)
in compound 1. The singly protonated phosphonate group
(P1) is bidentate and connects with two La3+ ions. The fully
deprotonated phosphonate group (P2) is tridentate and is
bridged to three La3+ ions. Unlike that in compound 1, the
carboxylate group of the phosphonate ligand in compound
2 is deprotonated and forms a four-member chelating ring
[La(1)–O(2)–C(4)–O(1)] (Figure 3). The amine group is pro-
tonated as in compound 1.
N(1)···O(13)
N(1)···O(1w)#5 3.32(1)
Compound 3
La(1)–O(43)#1
La(1)–O(13)#2
La(1)–O(42)
La(1)–O(33)#1
La(1)–O(22)
La(1)–O(31)#3
La(1)–O(1w)
P(1)–O(13)
P(1)–O(11)
P(1)–O(12)
P(2)–O(22)
P(2)–O(23)
2.409(5)
2.430(5)
2.441(5)
2.466(5)
2.495(5)
2.575(6)
2.632(7)
1.490(4)
1.528(4)
1.533(5)
1.504(4)
1.517(4)
1.542(4)
1.496(5)
1.504(4)
P(3)–O(32)
P(4)–O(43)
P(4)–O(42)
P(4)–O(41)
C(10)–O(1)
C(10)–O(2)
O(1)···O(2w)#4 2.732(7)
O(2)···O(23)#5
O(4)···O(41)#6
O(11)···O(11)#7 2.474(8)
O(12)···O(23)#8 2.493(7)
O(21)···O(21)#2 2.606(8)
O(32)···O(41)#8 2.539(7)
N(2)···O(2w)
N(1)···O(3w)
1.574(4)
1.511(4)
1.515(4)
1.520(4)
1.196(8)
1.302(8)
2.700(8)
2.505(7)
P(2)–O(21)
P(3)–O(33)
P(3)–O(31)
2.782(8)
2.757(8)
Compound 4
Er(1)–O(12)
Er(1)–O(13)#2
Er(1)–O(42)
P(1)–O(11)
P(1)–O(12)
P(2)–O(22)
P(3)–O(32)
P(3)–O(31)
P(4)–O(43)
C(10)–O(1)
C(20)–O(4)
N(1)···O(32)#1
O(3)···O(11)#4
O(21)···O(22)#5
2.206(4)
2.230(4)
2.244(4)
1.512(5)
1.516(5)
1.499(4)
1.494(5)
1.564(5)
1.507(4)
1.192(12)
1.203(11)
2.680(7)
2.624(8)
2.558(6)
Er(1)–O(23)#1
Er(1)–O(33)#3
Er(1)–O(43)#1
P(1)–O(13)
P(2)–O(23)
P(2)–O(21)
P(3)–O(33)
P(4)–O(42)
P(4)–O(41)
C(10)–O(2)
C(20)–O(3)
N(2)···O(22)#1
O(11)···O(41)
2.208(4)
2.237(4)
2.258(4)
1.513(5)
1.495(5)
1.568(4)
1.504(4)
1.501(4)
1.556(5)
1.309(11)
1.323(11)
2.772(7)
2.535(7)
Figure 3. ORTEP representation of the selected unit of compound
2. The thermal ellipsoids are drawn at 50% probability. Symmetry
codes for the generated atoms: A) –x – 1/2, y, –z – 1/2; B) x +
1/2, –y, z; C) x + 1, y, z; D) –x – 1/2, y, z + 1/2; E) x – 1, y, z; F)
x – 1/2, –y, z.
The interconnection of La3+ ions by phosphonate li-
gands led to a (010) double layer (Figure 4). The thicknes
of the double layer is about 9.0 Å. Neighboring 2D layers
O(31)···O(32)#6 2.681(6)
Eur. J. Inorg. Chem. 2006, 2011–2019
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2013

S.-F. Tang, J.-L. Song, J.-G. Mao
FULL PAPER
are held together by weak hydrogen bonds among the layer with –C6H4–COOH moieties hanging on both sides
amine group, aqua ligand, and noncoordination phos- of the layer (Figure 6). Extensive intralayer and interlayer
phonate oxygen, as well as a weak van der Waals force hydrogen bonds further crosslink these layers into a 3D
(Table 1, Figure 4).
supramolecular network (Figure 6, Table 1). The lattice
water molecules are located at the voids of the structure
and are involved in hydrogen bonding (Figure 6, Table 1).
The interlayer distance of about 16.8 Å is significantly
larger than that in compound 1, which is due to the intro-
duction of the additional phenyl group into the phos-
phonate ligand.
Figure 4. View of the structure of compound 2 down the a axis.
The phosphonate tetrahedra are shaded in medium gray. La, C, N,
and O atoms are drawn as open, black, octand, and crossed circles,
respectively.
Compound 3 also features a layered structure. The asym-
metric unit of 3 consists of one La3+ ion, one {H4L2}–
anion, one {H3L2}2– dianion, an aqua ligand, and two lat-
tice water molecules (Figure 5). The La3+ ion is seven-coor-
dinate by six phosphonate oxygen atoms from five phos-
phonate ligands and an aqua ligand. The La–O distances
are in the range 2.409(5)–2.632(7) Å, which is comparable
to those in compounds 1 and 2. The {H4L2}– anion com-
posed of P(1) and P(2) is bidentate and bridges with two
La3+ ions; each phosphonate group is singly protonated, as
are the amine group and the carboxylate group. The
{H3L2}2– anion composed of P(3) and P(4) is tetradentate;
it forms an eight-member chelating ring with a La3+ ion,
and also bridges with two other La3+ ions. Only one phos-
phonate group is singly protonated; the amine group and
the carboxylate group are also protonated.
Figure 6. View of the structure of compound 3 down the a axis.
The phosphonate tetrahedra are shaded in grey. La, N, C, and O
atoms are represented by open, dark grey, black, and light grey
circles, respectively. Hydrogen bonds are drawn as dashed lines.
The structure of Er(H3L2)(H4L2) (4) features a 3D supra-
molecular network based on 1D erbium() phosphonate
chains. The asymmetric unit of 4 is composed of one Er3+
ion, one (H3L2)2– dianion, and one (H4L2)– anion. The Er3+
ion is octahedrally coordinated by six phosphonate oxygens
from six different phosphonate ligands (Figure 7). The Er–
O distances [2.280(2)–2.331(2) Å] are comparable to those
found in the other erbium() phosphonate.[16] The coordi-
nation modes for the (H3L2)2– dianion and (H4L2)– anion
are similar. One phosphonate group is monodentate
whereas the other is bidentate. The amine group and the
carboxylate group for both types of anion are singly pro-
tonated. The main difference between the two phosphonate
anions are that both phosphonate groups are singly proton-
ated for the (H4L2)– anion [O(31) and O(41)] whereas only
one phosphonate group is singly protonated for the
(H3L2)2– dianion [O(21)].
Each pair of Er3+ ions is bridged by a pair of phos-
phonate groups to form a 1D chain along the a axis. Such
chains are further interconnected by strong hydrogen bonds
between noncoordinated phosphonate oxygens into a (002)
layer. These hydrogen bonds are O(21)···O(22) 2.558(6) Å
(symmetry code: 1 – x, 3 – y, 1 – z) and O(31)···O(32)
2.681(6) Å (symmetry code: –x, 1 – y, 1 – z). The –CH2–
C6H4–COOH groups of the phosphonate ligands are hang-
ing on the interlayer space (Figure 8). Intrachain hydrogen
bonds are also formed between the amine group and non-
coordinated phosphonate oxygens, and between two nonco-
ordinated phosphonate oxygens (Table 1). The interlayer
Figure 5. ORTEP representation of the selected unit of compound
3. The thermal ellipsoids are drawn at 50% probability. Hydrogen
bonds are drawn as dashed lines. Symmetry codes for the generated
atoms: A: –x + 2, –y + 1, –z + 1; B) –x + 2, –y + 2, –z + 1; C)
–x + 1, –y + 1, –z + 1.
Adjacent La3+ ions are bridged by the above two types distance is about 14.3 Å, which is shorter than that of com-
of phosphonate anions into a (002) lanthanide phosphonate pound 3. These 2D layers are further interlinked by hydro-
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New Layered Lanthanide Carboxylate-Phosphonates
FULL PAPER
gen bonds between carboxylate oxygen and noncoordinated
phosphonate oxygen [O(3)···O(11) 2.624(8) Å, symmetry
code: 1 – x, 1 – y, –z].
When erbium() nitrate was used instead of erbium()
chloride, compound 5 was isolated. H5L2 was also oxidized
by the nitrate anion to a new ligand, H3L3 (Scheme 1). Such
in situ oxidation of the P–C bond has also been observed
during the hydrothermal reactions of cobalt() nitrate with
H5L.[2,18] The asymmetric unit of 5 consists of one er-
bium() ion, a {H2L3}– anion, a {HL3}2– dianion, and an
aqua ligand (Figure 9). The erbium() ion is seven-coordi-
nate by six phosphonate oxygens from five phosphonate li-
gands and an aqua ligand. The Er–O distances range from
2.214(6) to 2.438(6) Å, which is comparable to those in
compound 4. The {HL3}2– dianion is tetradentate; it forms
a chelating ring with an erbium() ion [Er(1)–O(21)–P(2)–
O(22)] and also bridges with two other erbium() ions
[Er(1b) and Er(1c)]. The phosphonate group is fully depro-
tonated whereas the amine group remains protonated. The
{H2L3}– anion is bidentate and bridges with two erbium()
Figure 7. ORTEP representation of the selected unit of compound
4. The thermal ellipsoids are drawn at 50% probability. Hydrogen
bonds are drawn as dashed lines. Symmetry codes for the generated
atoms: A) 1 + x, y, z; B) 2 – x, 1 – y, 1 – z; C) 2 – x, 2 – y, 1 – z;
D) –1 + x, y, z.
Figure 8. An erbium() phosphonate inorganic chain along the a axis (a) and view of the structure of compound 4 down the a axis (b).
The ErO6 octahedra and phosphonate tetrahedra are shaded in dark gray and medium gray, respectively. N, C, and O atoms are repre-
sented by octand, black, and crossed circles, respectively.
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S.-F. Tang, J.-L. Song, J.-G. Mao
FULL PAPER
Figure 9. ORTEP representation of the selected unit of compound 5. The thermal ellipsoids are drawn at 50% probability. Symmetry
codes for the generated atoms: A) –x, –y + 2, –z + 1; B) –x – 1, –y + 1, –z + 1; C) –x, –y + 1, –z + 1.
ions using two oxygen atoms [O(12) and O(13)]. The third tation (Figure 11a), all of which can be attributed to the
4
phosphonate oxygen and the amine group are protonated 4I13/2 Ǟ I15/2 transition for the Er3+ ion.[16] The splitting
and noncoordinated. The carboxylate groups in both types of the 4I13/2 Ǟ 4I15/2 transition into several sub-bands is due
of anions are noncoordinated.
to the low symmetry of the coordination geometry around
the Er3+ ion (C1). The luminescence properties of com-
pound 5 are very interesting. Under emission of 330 nm,
the excitation spectrum of compound 5 displays one weak
The Er3+ ions in compound 5 are bridged by phos-
phonate groups of ligands into a (002) inorganic layer (Fig-
ure 10). Within the layer, Er2O2 rings and Er(–O–P–O–)2Er
rings can be found. Neighboring 2D layers are further inter-
linked by hydrogen bonds between carboxylate groups.
These hydrogen bonds are O(1)···O(4) 2.614(13) Å and O(2)···
O(3) 2.585(13) Å (symmetry codes are the same for both
bonds: 1 + x, 1 + y, –1 + z). The interlayer distance of
about 21.6 Å is the largest among five compounds, because
the carboxylate groups in other compounds are directly hy-
drogen bonded to a neighboring inorganic layer, whereas
the interlayer hydrogen bonding in compound 5 is between
two hanging organic groups (head to head).
Figure 10. View of the structure of compound 5 down the a axis.
The phosphonate tetrahedra are shaded in medium gray. Er, C, N,
and O atoms are drawn as open, black, octand, and crossed circles,
respectively. Hydrogen bonds are shown as dashed lines.
Based on X-ray powder diffraction studies, compounds
2–5 are prepared as single phases. The measured patterns
are in good agreement with those simulated from single-
crystal structures (see Supporting Information).
The solid-state luminescent properties of compounds 4
and 5 were investigated at room temperature. The emission
spectrum of compound 4 shows three strong near IR emis-
Figure 11. Luminescence spectra for compounds 4 (a) and 5 (b) at
sion bands at 1477, 1541, and 1561 nm under 520 nm exci- room temperature.
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New Layered Lanthanide Carboxylate-Phosphonates
FULL PAPER
absorption peak at 324 nm and a very strong absorption phosphonate ligands. The total weight loss at 1000 °C is
peak at 408 nm. Surprisingly, compound 5 shows no near 34.3% and the final residue was not characterized.
IR emission band under our experimental conditions. Un-
der excitation of 408 nm, the emission spectrum of com-
pound 5 exhibits a very broad band with two maximum Conclusion
intensity peaks at 460 and 571 nm (Figure 11b), which may
be assigned to the intraligand π–π* fluorescence. The ab-
sence of near IR emission is probably due to the quenching
In summary, the hydrothermal syntheses, crystal struc-
tures, and luminescent properties of five new lanthanide()
phosphonates with layered structures have been described.
effect of the luminescent state by high-frequency vibrating
Results from this and previous work indicate that we can
water molecules.[16a]
greatly improve the solubility and crystallinity of lanthanide
phosphonates by attaching amino acid moiety to the phos-
phonic acid or introducing a second ligand such as oxalate
TGA curves for compounds 2–5 are shown in Figure 12.
TGA curves of compound 2 indicate one main step of
weight loss. The weight loss between 260 and 620 °C corre-
or carboxylate-sulfonate. The counteranion used plays an
sponds to the release of water molecules and the combus-
important role. It affects the acidity of the solution and the
tion of the phosphonate ligand. The weight loss is about
extent of deprotonation of phosphonate ligands, as well as
20.5%. There is small weight loss starting from 800 °C,
the coordination mode a phosphonate ligand adopts. Oxid-
which can be attributed to the further decomposition of the
izing anions such as nitrate groups may also trigger the in
situ oxidation of P–C bonds. Furthermore, the so-called
compound. The total weight loss at 1000 °C is 24.4%. The
residue was not characterized. Compound 3 shows no obvi-
“lanthanide contraction” is also important. Heavy lantha-
ous weight loss before 135 °C. The weight loss in the tem-
nide ions usually have smaller coordination numbers than
the light ones, which may result in different coordination
perature range of 135–270 °C corresponds to the release of
two lattice water molecules and an aqua ligand. The ob-
modes for the phosphonate ligands. However, more system-
served weight loss of 6.8% is close to the calculated value
atic studies are still needed to further understand the chem-
istry of lanthanide phosphonates.
(6.2%). Then the compound decomposes continuously up
to 1000 °C, which corresponds to the combustion of or-
ganic groups. The total weight loss at 1000 °C is 48.6% and
the residue was not characterized. Compound 4 is stable up
to 355 °C. Then it exhibits a sharp weight loss between 355
Experimental Section
Materials and Methods: (H2O3PCH2)2NCH2CO2H (H5L1) and 4-
and 575 °C with a weight loss of 23.8%. The total weight
at 1000 °C is 34.3% and the final residue was not charac-
terized. TGA curves for compound 5 display two main
steps of weight losses. There is no obvious weight loss be-
fore 280 °C. The weight loss in the range of 280–340 °C
corresponds to the release of an aqua ligand and the de-
composition of the two carboxylate groups of two phos-
phonate ligands. The observed weight loss of 13.4% is
slightly smaller than the calculated one (14.5%). The sec-
ond weight loss covers a temperature range from 340 to
650 °C, which corresponds to further combustion of the
HO2C–C6H4–CH2N(CH2PO3H2)2 (H5L2) were prepared by
a
Mannich-type reaction according to the procedures described pre-
viously.[6] All other chemicals were obtained from commercial
sources and used without further purification. Elemental analyses
were performed on a Vario EL III elemental analyzer. Thermograv-
imetric analyses were carried out on a NETZSCH STA 449C unit
at a heating rate of 15 °C/min under nitrogen. IR spectra were re-
corded with a Magna 750 FTIR spectrometer photometer as KBr
pellets in the range 4000–400 cm–1. Photoluminescence analyses
were performed on an Edinburgh FLS920 fluorescence spectrome-
ter. X-ray powder diffraction patterns (Cu-Kα) were collected in a
sealed glass capillary on a XPERT-MPD θ–2θ diffractometer.
Preparation of La(H2L1)(H2O)2·H2O (1): A mixture of LaCl3·6H2O
(176.7 mg, 0.5 mmol), H5L1 (131.6 mg, 0.5 mmol), and 2-hydroxy-
pyridine (95.1 mg, 1.0 mmol) in 10 mL of distilled water was sealed
into an autoclave equipped with a Teflon liner (25 mL) and then
heated at 120 °C for 4 days. The initial pH value of the resultant
solution was 3.0. Colorless plate-shaped crystals of 1 were col-
lected. Yield: 11.3 mg (5%, based on La). Based on the X-ray pow-
der diffraction study, the majority of impurity was powder of com-
pound 2. Efforts to prepare a single-phase product of compound 1
were unsuccessful.
Preparation of La(H2L1)(H2O) (2):
A mixture of La(OH)3
(189.9 mg, 1.0 mmol) and H5L1 (263.1 mg, 1.0 mmol) in 10 mL of
distilled water was sealed into a bomb equipped with a Teflon liner
(25 mL) and then heated at 150 °C for 4 days. The initial and final
pH values of the resultant solution were 3.5 and 2.5, respectively.
Colorless plate-shaped crystals of 2 were collected. Yield: 250 mg
(60%, based on La). IR (KBr): ν = 3359 m, 3139 m, 1607 m, 1448
˜
w, 1407 s, 1371 m, 1305 w, 1214 m, 1164 m, 1083 vs, 1008 m, 974
Figure 12. TGA curves for 2 (thick line, black), 3 (thin line, black),
4 (light grey line), and 5 (medium grey line).
w, 949 w, 844 w, 768 w, 720 m, 587 w, 496 w, 468 w, 447 w cm–1.
Eur. J. Inorg. Chem. 2006, 2011–2019
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S.-F. Tang, J.-L. Song, J.-G. Mao
C4H10LaNO9P2 (416.98): calcd. C 11.52, H 2.42, N 3.36; found C unique (Rint = 0.0307). R1 = 0.0236, wR2 = 0.0612 [I Ͼ 2σ(I)], R1
FULL PAPER
11.60, H 2.54, N 3.28.
= 0.0263 and wR2 = 0.0627 (all data) and final Gof = 1.056.
Preparation of La(H4L2)(H3L2)(H2O)·2H2O (3): A mixture of
La(OH)3 (56.98 mg, 0.3 mmol) and H5L2 (169.6 mg, 0.5 mmol) in
10 mL of distilled water was sealed into a bomb equipped with a
Teflon liner (25 mL) and then heated at 145 °C for 4 days. The
initial and final pH values of the resultant solution were 4.5 and
2.5, respectively. Colorless plate-shaped crystals of 3 were collected.
Crystal Data for 2: C4H10LaNO9P2 (416.98), orthorhombic, space
group Pca21, T = 293(2) K, a = 9.9649(13), b = 10.5833(15), c =
10.5288(15) Å, V = 1110.4(3) Å3, Z = 4, dcalcd = 2.494 Mg/m3,
F(000) = 800, µ(Mo-Kα) = 4.173 mm–1, 8258 reflections collected,
2418 unique (Rint = 0.0891). R1 = 0.0644, wR2 = 0.1039 [I Ͼ 2σ(I)],
R1 = 0.0793 and wR2 = 0.1113 (all data) and final Gof = 1.142.
Yield: 121.6 mg (56%, based on H L2). IR (KBr): ν = 3480 m,
˜
5
Crystal Data for 3: C20H33LaN2O19P4 (868.27), triclinic, space
3387 m, 3219 m, 3020 w, 3010 w, 2614 w, 1697 s, 1642 m, 1460 w,
1403 m, 1321 w, 1274 w, 1163 m, 1115 vs, 991 m, 931 m, 825 w,
761 m, 644 w, 560 m, 535 m, 484 w, 451 w cm–1. C20H33LaN2O19P4
(868.27): calcd. C 27.65, H 3.83, N 3.23; found C 27.70, H 3.92, N
3.18.
Preparation of Er(H3L2)(H4L2) (4): A mixture of ErCl3·6H2O
(95.4 mg, 0.25 mmol) and H5L2 (84.8 mg, 0.25 mmol) in 10 mL of
distilled water was sealed into an autoclave equipped with a Teflon
liner (25 mL) and heated at 145 °C for 5 days. The initial and final
pH values of the resultant solution were 3.5 and 2.0, respectively.
Pink brick-shaped crystals of 4 were collected. Yield: 147 mg (70%,
¯
group P1, T = 293(2) K, a = 8.246(17), b = 10.58(2), c = 16.79(3) Å,
α = 90.34(3), β = 90.21(4), γ = 93.52(3)°, V = 1461(5) Å3, Z = 2,
dcalcd = 1.973 Mg/m3, F(000) = 872, µ(Mo-Kα) = 1.772 mm–1, 11453
reflections collected, 6609 unique (Rint = 0.0456). R1 = 0.0542, wR2
= 0.1036 [I Ͼ 2σ(I)], R1 = 0.0722 and wR2 = 0.1143 (all data) and
final Gof = 1.088.
Crystal Data for 4: C20H26ErN2O16P4 (841.57), triclinic, space
¯
group P1, T = 293(2) K, a = 7.9178(7), b = 12.5608(5), c =
15.3008(7) Å, α = 110.453(7), β = 90.296(12), γ = 90.586(13)°, V =
1425.66(15) Å3, Z = 2, dcalcd = 1.960 Mg/m3, F(000) = 832, µ(Mo-
Kα) = 3.247 mm–1, 11127 reflections collected, 6439 unique (Rint
=
based on Er). IR (KBr): ν = 3494 m, 3114 m, 2674 w, 2557 w, 1705
˜
0.0456). R1 = 0.0528, wR2 = 0.0984 [I Ͼ 2σ(I)], R1 = 0.0684 and
wR2 = 0.1072 (all data) and final Gof = 1.107.
s, 1401 m, 1318 m, 1206 m, 1113 vs, 1020 m, 994 m, 951 m, 908 w,
879 w, 820 w, 808 w, 763 m, 719 m, 681 w, 637 w, 582 m, 515 w,
493 w, 465 w, 413 w cm–1. C20H26ErN2O16P4 (841.57): calcd. C
28.54, H 3.11, N 3.33; found C 28.50, H 3.17, N 3.39.
Crystal Data for 5: C20H23ErN2O13P2 (728.60), triclinic, space
¯
group P1, T = 293(2) K, a = 5.752(4), b = 9.382(5), c =
22.050(15) Å, α = 101.507(16), β = 92.62(2), γ = 98.155(19)°, V =
Synthesis of Er(HL3)(H2L3)(H2O) (5): A mixture of Er(NO3)3·
6H2O (230.70 mg, 0.5 mmol), H5L2 (169.6 mg, 0.5 mmol), and 2-
hydroxypyridine (95.10 mg, 1.0 mmol) in 10 mL of distilled water
was sealed into a bomb equipped with a Teflon liner (25 mL) and
then heated at 120 °C for 4 days. The initial and final pH values of
the resultant solution were 3.0 and 2.5, respectively. Light yellow
brick-shaped crystals of 5 were collected. Yield: 91 mg (25%, based
1151.0(12) Å3, Z = 2, dcalcd = 1.715 Mg/m3, F(000) = 718, µ(Mo-
Kα) = 3.839 mm–1, 3176 reflections collected, 2217 unique (Rint
=
0.0277). R1 = 0.0440, wR2 = 0.1207 [I Ͼ 2σ(I)], R1 = 0.0469 and
wR2 = 0.1239 (all data) and final Gof = 1.033.
CCDC-295013 to -295017 (for 1–5) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
on Er). IR (KBr): ν = 3494 m, 3116 m, 2674 w, 2557 w, 1686 s,
˜
1611 m, 1579 w, 1511 w, 1453 m, 1430 m, 1324 m, 1296 m, 1239
m, 1175 w, 1104 vs, 1025 m, 994 m, 951 m, 908 w, 879 w, 820 w,
791 w, 763 m, 719 w, 681 w, 641 w, 575 m, 506 w, 493 w, 465 w,
414 w cm–1. C20H23ErN2O13P2 (728.60): calcd. C 29.59, H 3.18, N
7.51; found C 30.08, H 3.26, N 7.46.
Supporting Information (see footnote on the first page of this arti-
cle): X-ray powder diffraction patterns for compounds 2–5.
Acknowledgments
Single-Crystal Structure Determination: Data collections for com-
pounds 1–5 were performed with a Rigaku Mercury CCD dif-
fractometer equipped with graphite-monochromated Mo-Kα radia-
tion (λ = 0.71073 Å). Intensity data were collected by the narrow
frame method at 293 K. The data sets were corrected for Lorentz
and polarization factors as well as for absorption by the multiscan
technique.[18] All five structures were solved by the direct methods
and refined by full-matrix least-squares fitting on F2 by SHELX-
97.[19] All non-hydrogen atoms were refined with anisotropic ther-
mal parameters, except for C(1), C(4), and O(11) in compound 2,
and C(21) in compound 5, which were refined isotropically. The
lattice water molecule in compound 1 was disordered over two ori-
entations [O(3w) and O(3wЈ)], with an interatomic distance of
0.932 Å. Each orientation was refined with 50% occupancy. Hydro-
gen atoms attached to carbon atoms, amine groups, and phos-
phonate groups were located at geometrically calculated positions
and refined with isotropic thermal parameters. The protonation for
the amine groups as well as phosphonate groups was based on P–
O distances and charge balance. Hydrogen atoms for water mole-
cules were not included in refinements.
This work was supported by the National Natural Science Founda-
tion of China (20371047, 20521101) and NSF of Fujian Province
(E0420003).
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Published Online: March 27, 2006
Eur. J. Inorg. Chem. 2006, 2011–2019
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