A chiral tetrahedral framework with tetrahedral guests for catalysis and photoluminescence

Article abstract of DOI:10.1021/cg400769p

Presented here is a chiral three-dimensional indium(III)-organic compound [In(5-Aip)₂]·(TPP)·4H₂O (1; 5-Aip = 5-aminoisophthalate, TPP = tetraphenylphosphonium). The structure of 1 features an unusual tetrahedral anionic framework containing tetrahedral TPP guests. This compound shows interesting photoluminescent properties and notable catalytic activity on the diethylzinc addition to benzaldehyde. The results reveal that the employment of tetrahedral TPP cations as guests can not only direct the formation of a tetrahedral framework but also help on the improvement of physical properties.

Full text of DOI:10.1021/cg400769p

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Communication
A chiral Tetrahedral Framework with Tetrahedral
Guests for Catalysis and Photoluminescence
Yan-Fei Chen, Yun-Cui Ma, and Shu-Mei Chen
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg400769p • Publication Date (Web): 09 Sep 2013
Downloaded from http://pubs.acs.org on September 18, 2013
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A chiral Tetrahedral Framework with Tetrahedral Guests for
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Yan-Fei Chen, Yun-Cui Ma, Shu-Mei Chen
College of Chemistry & Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350108, P. R. China
Supporting Information Placeholder
.
.
ABSTRACT: Presented here is a chiral threeꢀdimensional Indium(III)ꢀorganic compound [In(5ꢀAip) ] (TPP) 4H O (1; 5ꢀAip=5ꢀ
2
2
aminoisophthalate, TPP = tetraphenylphosphonium). The structure of 1 features an unusual tetrahedral anionic framework
containing tetrahedral TPP guests. This compound shows interesting photoluminescent properties and notable catalytic activity on
the diethylzinc addition to benzaldehyde. The results reveal that the employment of tetrahedral TPP cations as guests can not only
direct the formation of tetrahedral framework, but also help on the improvement of physical properties.
Metalꢀorganic frameworks (MOFs) or porous coordination
polymers (PCPs) have recently attracted considerable interest
not only for their potential applications in gas storage,
separation, sensing and heterogeneous catalysis, but also for
crystallization process tends to centric symmetry. Meanwhile,
template agent also plays an important role in the design and
synthesis of the chiral architectures.
11
In this work, we report a new chiral Indium(III)ꢀorganic
1
,
3
.
.
fascinating architectures and topologies.
Templated
compound
[In(5ꢀAip) ] (TPP) 4H O
(1;
5ꢀAip=5ꢀ
2
2
synthesis is of great importance in the design and syntheses of
aminoisophthalate) based on achiral 5ꢀAip ligand and
tetrahedral TPP guests. Compound 1 features a tetrahedral
framework with 4ꢀconnected dia topology and shows
interesting photoluminescent properties and notable catalytic
activity on the diethylzinc addition to benzaldehyde.
4
,
5
functional materials based on MOFs.
Some
tetraalkylammonium cations have been widely used to assist the
formation of MOFs. However, the tetraphenylphosphonium (=
TPP) cation has never been considered to fabricate this aim in
the past years. Actually, the TPP cation with tetrahedral
configuration is good for a template agent to regulate and
control the channel environment of MOFs. Moreover, it has
potential catalytic and photoluminescent properties because of
the presence of rich benzene rings. TPP as a auxiliary catalyst
was used in some organic reaction and had a remarkable
1
2
Crystals of 1 were synthesized by solvothermal method
and structurally characterized by singleꢀcrystal Xꢀray
1
3
diffraction, thermogravimetric analysis (TGA) (Figure S6),
IR and circular dichroism spectrum (CD). Compound 1
crystallizes in the chiral space group I4 22, indicating the
1
chiral nature of each single crystal. The phase purity of 1 was
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effect.
characterized by powder Xꢀray diffraction (PXRD, Figure S5).
3+
In addtion, MOFꢀbased catalysis has become a hot topic in
recent years, but it is still in an immature phase and many
detailed catalytic mechanisms are worthy of further
In the structure of 1, each In ion adopts 4ꢀconnected
pattern by coordinating to eight oxygen atoms from four 5ꢀAip
ligands. The InꢀO distances are ranging from 2.192(6) to
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exploration. MOFꢀbased catalysis have some typical
2.378(4) Å (Figure 1). Each 5ꢀAip ligand acts as a ꢁ ꢀlinker to
2
3+
characteristics. One promising case is the presence of active
metal centers in the structure. For example, the catalytic
activity of the wellꢀknown HKUSTꢀ1 and MILꢀ101 in the
cyanosilylation of benzaldehyde was due to the wellꢀdefined8
accessible Lewis acidic sites exposed to the inner surface.
Therefore, how to produce accessible active metal centers may
be the key. Other effective approach is to construct inorganic
building blocks with possible unsaturated coordination sites,
bridge two In ions. The resulting tetrahedral In(COO) units
4
are further connected by the aromatic rings of the 5ꢀAip
ligands to form an anionic 3D framework, the whole large
open channels are fully occupied by guest TPP cations (Figure
2). In this way, the structure can be topologically represented
as a 4ꢀconnected dia net. The guest TPP cations trapped into
the open anionic framework of 1, to the best of our knowledge,
is truly unusual and rarely known in other MOFs. That also
takes some significant properties for compound 1.
typically similar to the paddleꢀwheel Cu (COO)4 unit
2
combined with terminal molecules, the removal of which leads
to active metal sites. Another effective mean is to incorporate
<insert Figure 1 here>
<insert Figure 2 here>
8
catalytic active metal sites into organic ligands, such as
metalloporphyrins and other metalloligands with Schiffꢀbase
unit or binaphthyl unit.
To investigate the chiral nature of 1, solidꢀstate CD
measurements on a MOSꢀ450 instrument were performed on
solid material in KCl plates. We randomly selected different
bulk crystal samples to measure the CD spectra. As shown in
Figure 3, all measurements produce the same effect. There are
obvious cottonꢀeffect at ca. 230 nm. These results demonstrate
that bulk sample of 1 is enantoriched or homochiral.
<insert Figure 3 here>
9
Of particular interest is to construct chiral MOFs for
1
0
catalysis applications. Both enantiopure and achiral organic
molecules can be employed to form the chiral architectures via
the spatial organization of basic structural building blocks into
1
1
chiral space groups. However, the generation of chirality
from achiral precursor is still unpredictable because the
The photoluminesent emission spectra of compound 1 and
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TPP Br were measured in the solid state at room temperature
Figure 4). Compound 1 exhibits one intense emissions at 400
enhancing photoluminescence, and catalyzing. The results
demonstrated that TPP cation may serve as a good template
agent for the construction of new functional materials.
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(
nm upon irradiation of ultraviolet light at λ = 371 nm. The
emission maximum wavelength of TPP Br reaches to 504 nm
at λex = 319 nm. Compared to TPP Br, the πꢂꢂꢂπ interactions in
ex
.
.
ASSOCIATED CONTENT
1
are strengthened including ligandꢀtoꢀligand, ligandꢀtoꢀTPP
Supporting Information. additional Figures, Gas Chromatograph,
TGA, IR, powder Xꢀray diffraction patterns and CIF file. This
material is available free of charge via the Internet at
http://pubs.acs.org.
.
and TPPꢀtoꢀTPP. The emissions of TPP Br may be assigned to
the πꢂꢂꢂπ electronic transition between the benzene ring (504
nm) and the charge transfer (384nm) involving with benzene
ringꢂꢂꢂP [π→ 3d] which have 3d free orbital. The emission
spectra of 1 and TPP Br imply that the properties of their
excited states are mainly related to their own coordination
factors, such as the coordination between P and C atoms in
TPP, or other intramolecular interactions. Compared to the
free TPP group in TPP Br, all TPP groups in compound 1 are
regularly arranged in the pore spaces. Thus, the benzene rings
1
4a
.
AUTHOR INFORMATION
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Corresponding Author
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*Eꢀmail: csm@fzu.edu.cn
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ACKNOWLEDGMENTS
This work is supported by NSFC (21101027), NSF of Fujian
Province (2011J05025), and Research Fund for the Doctoral
Program of Higher Education of China (20113514120002).
of TPP are limited on rotation, and compound 1 produces
different photoluminescent emission from TPP Br.
.
<insert Figure 4 here>
REFERENCES
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(Figure 5a). Actived catalyst 1 (24 mg) dried under vacuum at
100 °C for 8 h was placed in a 25 mL Schlenk flask and then
vacuumized for 10 min. The nꢀhexane (2 mL) solvent was
added via syringe under nitrogen. After the mixture was stirred
for 30 min, benzaldehyde (25ꢃL) and diethylzinc (in nꢀhexane,
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nitrogen at 25 C. In a certain time interval, a small amount of
sample was taken out and quenched with saturated NH Cl
4
solution. The composition of the reaction mixture was
determined by GC analysis. We can observe racemic
phenylpropanol (Rꢀ and Sꢀ) with the same yield in the products,
indicating that there is no enatioselectivity. After 24 h, the
reaction leaded to a 54.6% conversion of benzaldehyde and it
is basically stopped (Figure 5b). The PXRD pattern of 1 after
catalysis is consistent with that of the asꢀsynthesized sample,
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other reported MOF catalysts with active metal centers,
compound 1 has no active metal centers in the structure,
because all In(III) centers in 1 are fully coordinated by the
carboxylate groups. We had already taken TPP Br to do the
contrast test. The results indicated that TPP Br has a good
homogeneous catalytic effect for this reaction (Figure S4).
Thus, we speculated that the guest TPP cations in 1 might play
a major role in this catalytic process. Mass spectrometry (MS)
was employed to check the solution after catalytic reaction, in
order to examine the possibility of leaking of the TPP cations
into the solution. Obvious peak of 339.5 corresponding to the
TPP cation was found (Figure S8), demonstrating the presence
of the TPP cations in the solution. This result reveals that
compound 1 is a special homogeneous catalyst for this
reaction.
8
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<
insert Figure 5 here>
In summary, we have successfully constructed a novel
chiral coordination polymer with diaꢀtype structure by
employing
tetraphenylphosphonium bromide. Compound 1 has notable
catalytic activity on the addition reaction of diethylzinc to
benzaldehyde. The TPP cation reported here presents three
special roles: balancing charges and supporting frameworks,
achiral
5ꢀaminoisophthalic
acid
and
2
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(
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1
1
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1
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(
2
011, 9, 3717. (e) Zhang, J.; Wu, T.; Chen, S. M.; Feng, P. Y.; Bu, X. H.
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12) Synthesis of In(5-Aip)2(TPP). A mixture of In(PO
(
3 3
) (0.2 mmol),
5ꢀAip (0.4mmol), TPPB(0.2mmol) and DMF (5ml) were sealed in a 20
o
mL vial , heated at 100 C for 3 days under autogenous pressure. After the
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reaction was cooled to room temperature, colorless crystals were produced
ꢀ
1
(
1
yield: 31%, based on In). IR (solid KBr pellet v/cm ): 3450w, 3345w,
659s, 1560m, 1379s, 747m.528m (Figure S7).
13) Crystal data for 1: C40 12P, M = 884.51, Tetragonal, a = b =
11.9482(3) Å, c = 30.657(2) Å, V = 4376.5(3) Å , T = 293(2) K, space
group I4 22, Z = 4, 4354 reflections measured, 1514 independent
reflections (Rint = 0.0330). The final R = 0.1162 (I > 2σ(I)). The final
(
2
H38InN O
3
1
1
2
2
wR(F ) = 0.3521 (I > 2σ(I)). The goodness of fit on F was 1.148. The
crystallographic calculations were conducted using the SHELXLꢀ97
programs.
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Qiu, J. S.; Inorg. Chem., 2012, 51, 12389. (c) Choi, J. R.; Tachikawa, T.;
Fujitsuka, M.; Majima, T. J. Phys. Chem. Lett., 2010, 1, 1101.
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Chem. Commun., 2012, 48, 4489. (b) Nagai, A.; Koike, N.; Kudo, H.;
Nishikubo, T. Macromolecules, 2007, 40, 8129.
Figure 2. The 3D open framework of 1 containing TPP guests in the
channels.
Figure 1. The coordination environment in 1.
Figure 3. The solid state CD spectra of 1.
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Figure 4. Excitation and emission spectra of 1 and TPP Br in the solid
state at room temperature.
Figure 5. The change of phenylpropanol concentration with time for
compound 1.
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Presented here is a chiral threeꢀdimensional Indium(III)ꢀorganic compound with an unusual tetrahedral anionic framework
containing tetrahedral TPP guests, which shows interesting photoluminescent properties and notable catalytic activity on the
diethylzinc addition to benzaldehyde.
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