A chiral twofold interpenetrated diamond-like 3D In(III) coordination network with 4,4′,4″-phosphoryltribenzoate

Article abstract of DOI:10.1016/j.inoche.2009.09.031

A novel In(III) coordination complex, [In(ptc)(H₂O)]_n (H₃ptc = 4,4′,4″-phosphoryltribenzoic acid) (1), was synthesized under hydrothermal condition and characterized by single-crystal X-ray analysis, IR, X-ray powder diffr

Full text of DOI:10.1016/j.inoche.2009.09.031

Inorganic Chemistry Communications 12 (2009) 1238–1241
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
A chiral twofold interpenetrated diamond-like 3D In(III) coordination network with
4,40,400-phosphoryltribenzoate
*
Qiang Gao, Ming-Yan Wu, Lian Chen, Fei-Long Jiang, Mao-Chun Hong
State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
a r t i c l e i n f o
a b s t r a c t
A novel In(III) coordination complex, [In(ptc)(H2O)]n (H3ptc = 4,40,400-phosphoryltribenzoic acid) (1), was
synthesized under hydrothermal condition and characterized by single-crystal X-ray analysis, IR, X-ray
powder diffraction (XRD), thermogravimetric analysis (TGA) and solid-state photoluminescence. Com-
plex 1 crystallizes in a chiral P21 space group, In(III) ions are eight-coordinated and the ligand exhibits
a novel and unique tetrahedral coordination mode. The complex shows intense blue emission at
435 nm with the excitation of 330 nm.
Article history:
Received 10 July 2009
Accepted 28 September 2009
Available online 4 October 2009
Keywords:
Crystal structure
Indium(III)
4,40,400-Phosphoryltribenzoic acid
Chiral
Ó 2009 Published by Elsevier B.V.
The design and construction of metal–organic frameworks
(MOFs) are under intensive investigations in recent years due to
their potential applications in various research fields, such as gas
adsorption and separation, catalysis, magnetism, and lumines-
cence [1]. In order to obtain MOFs with desirable topologies and
properties, different metal ions were tested, and most concentra-
tions were focused on transition divalent metal ions [2]. We and
some other groups, however, are interested in the research of
one IIIA group metal ion, In(III) [3]. Compared to divalent transition
metal ions, which are usually four- or six-coordinated, In(III) ions
have the ability to adopt MO6, MO7, or even MO8 coordination
modes. Moreover, the increased valence charge of In(III) may also
show some influence on the resulting structure as it is postulated
that the incorporation of trivalent metal ions might create diverse
structures different from those containing divalent metal ions.
On the other hand, multifunctional organic ligands are well
exploited. Many carboxylate ligands with high symmetry have
been synthesized and studied [4]. The results indicate that they
have great advantages over those ligands with low symmetry in
constructing geometrically consummate polyhedra with large pore
sizes. Among them trigonal carboxylate ligands bearing C3 symme-
try are intensively investigated. For example, Yaghi’s group and
Zhou’s group have independently designed several threefold sym-
metric tricarboxylates such as 1,3,5-benzenetribenzoate (BTB) and
1,3,5-tris[40-carboxy(1,10-biphenyl-4-yl)]-benzene (TCBPB) and
plenty of porous MOFs with excellent gas adsorption properties
have been obtained by utilizing these ligands. Inspired by these re-
search results, we intended to exploit another ligand, 4,40,400-phos-
phoryltribenzoic acid (H3ptc) [7], which can be regarded as a
derivative of these ligands. Except for the three C3-related carbox-
ylic groups, there is one more coordination atom O of the P@O
bond, which may impose great influence on the final framework.
Up to now, only a few results have been documented on the coor-
dination research of this ligand [5]. And the research was all fo-
cused on divalent traditional metal ions, such as Co(II), Mn(II)
and Zn(II). However, to the best of our knowledge, the investiga-
tion with main group metal ions and trivalent metal ions is still
unprecedented.
Hydrothermal reaction of H3ptc and indium(III) chloride at
150 °C results in the formation of colorless block crystals of 1 [6].
A single-crystal X-ray diffraction study [8] reveals complex 1 crys-
tallizes in a chiral P21 space group and In(III) ion exhibits an unu-
sual high coordination number of eight [3a]. As shown in Fig. 1, the
center metal ion is coordinated by six oxygen atoms from three
carboxylate groups of three individual ptc ligands, as well as one
oxygen atom from the P@O of the fourth ligand and one water mol-
ecule, forming a dodecahedron motif. The In–O bond lengths range
from 2.103 (4) Å to 2.550 (8) Å, which are comparable with those
reported [3]. The ligand uses all seven coordinating oxygen atoms
available in a j2 j2 j2 j1
- - - -l4 coordination mode, with all three
carboxylate groups in chelating coordination mode and the oxygen
atom (O7) from P@O bond in monodentate coordination mode
(Scheme 1). As far as we know, such a coordination mode is
unprecedented. There are in all four types of coordination modes
of H3ptc ligand (Scheme S1), and none of them uses all of the seven
oxygen atoms to engage in the coordination. The difference may be
attributed to the abundant coordination modes and increased va-
lence charge of In(III).
* Corresponding author. Tel.: +86 591 8379 2460; fax: +86 591 8379 4946.
E-mail address: hmc@fjirsm.ac.cn (M.-C. Hong).
1387-7003/$ - see front matter Ó 2009 Published by Elsevier B.V.
doi:10.1016/j.inoche.2009.09.031

Q. Gao et al. / Inorganic Chemistry Communications 12 (2009) 1238–1241
1239
Fig. 1. The coordination environment around In(III) in 1 with the thermal ellipsoid at the 30% probability level. Symmetry code: (A) x, y, z ꢀ 1; (B) x, 1 + y, z; (C) x ꢀ 1, y, z.
give rise to the final 3D framework. The structure can be better
understood from topological perspective. The metal centers and
the ligands both serve as distorted tetrahedral 4-connected nodes
and the distances are 3.538 Å, 8.665 Å, 8.693 Å and 8.722 Å, respec-
tively. The connection between these nodes produces a well con-
structed 3D diamond-like network (Fig. 2). There are large
channels in the framework along the three axes due to the rigid
conformation of the ligand. In order to fill the large void space, an-
other diamond net interpenetrates with this one, thus forming a
twofold interpenetrating structure (Fig. 3). As a self-dual net, inter-
penetrating diamond-like nets have been well studied and exam-
ples are known of degrees of interpenetration ranging from two-
to tenfold [10]. According to the classification of interpenetration
topology by Blatov et al., the complex belongs to class IIa, that is,
Scheme 1. Coordination mode of H3ptc ligand in the article.
the individual nets are related by means of a full interpenetration
symmetry element. In this case, the twofold dia nets are generated
by a 21 screw axis and the nonetranslational degree Zn = 2. Up to
In this way, the ligand joints four metal centers in four direc-
tions that resemble a tetrahedron. This coordination motif is dom-
inated by the conformation of the ligand. Moreover, the metal
centers share similar coordination motif with the ligands, which
now, there are only two examples of this type [10]. The whole
framework is thus chiral. These two nets are interacted through
two groups of hydrogen bonds between the coordination water
molecules (O8) and two oxygen atoms (O2 and O6) of two carbox-
Fig. 2. (a) Schematic representation of the diamond-like net along c-axis. Hydrogen atoms are omitted for clarity. (b) Topological representation of 1. Color code: green, In;
pink, P; red, O; gray, C. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

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Q. Gao et al. / Inorganic Chemistry Communications 12 (2009) 1238–1241
Fig. 3. (a) Schematic representation of the twofold interpenetration of 1 along b-axis. Hydrogen bonds are shown in dashed lines. Topological representation of
interpenetration along b-axis (b) and c-axis (c).
ylate groups. The O8ꢁ ꢁ ꢁO2 and O8ꢁ ꢁ ꢁO6 distances are 2.803(7) Å
and 2.871(8) Å, the angles of O8–H8Aꢁ ꢁ ꢁO2 and O8–H8Bꢁ ꢁ ꢁO6 are
150.9° and 140.9°, respectively.
The FT-infrared (IR) spectrum of 1 shows a broad absorption at
3448 cmꢀ1 which can be attributed to the presence of water mol-
ecules. The absorption range from 1396 to 1703 cmꢀ1 is consistent
with that of the carboxylate groups. Furthermore, the strong peaks
at 1268 cmꢀ1, 1166 cmꢀ1, 1106 cmꢀ1, 707 cmꢀ1 and 576(m) cmꢀ1
justify the presence of P@O bond. The X-ray powder diffraction
(XRD) of 1 was measured at room temperature. The peak positions
of simulated XRD pattern matches with the observed, indicating
that the complex is obtained in pure phase (Fig. S1). The thermal
stability of 1 was investigated. As illustrated in Fig. S2, the loss of
coordination water molecules occurred in the range of 60–150 °C
(calcd 3.33%, found 3.34%), then the complex underwent decompo-
sition in two steps. The first step corresponds to a weight loss of
42.3%, indicating the partial decomposition of the ligand, the sec-
ond step suggests a weight loss of 15.56%, implying the total
decomposition of the ligand, which yields the final residual of
the mixture of In2O3 and P2O5 (calcd 38.70%, found 38.81%).
The photoluminescence property of 1 was recorded at room
temperature and 10 K in the solid state. As shown in Fig. 4, Com-
plex 1 exhibits intense pure blue photoluminescence with an emis-
sion maximum at ca. 435 nm upon excitation at 330 nm, and the
blue emission could even be observed by naked eyes under irradi-
ation of ultraviolet light with the wavelength of 365 nm. At 10 K,
the emission spectrum displays a sharp peak at ca. 441 nm with
upon excitation at 330 nm, which shows a negligible shift of
6 nm in comparison with that at room temperature. The free
H3ptc ligand exhibits a similar emission at ca. 450 nm upon excita-
Fig. 4. Solid-state photoluminescent spectrum of 1 at room temperature and 10 K.
tion at 330 nm (Fig. S3). So the emission of 1 can be attributed to
intraligand charge transfer.
Conclusion
In summary, a chiral twofold interpenetrated diamond-like 3D
In(III) coordination network with 4,40,400-phosphoryltribenzoate
was hydrothermally synthesized. The results indicate that H3ptc li-

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1241
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