Enantioselective Separation over a Chiral Biphenol-Based Metal-Organic Framework

Article abstract of DOI:10.1021/acs.inorgchem.8b00948

A chiral porous 3D metal-organic framework (MOF) is constructed from an enantiopure carboxylate ligand of 1,1′-biphenol, which can be utilized as adsorbent for the separation of aromatic alcohols and sulfoxides with enantioselectivity of up to 99.4%. Single-crystal X-ray diffraction analysis reveals the binding sites and host-guest interactions clearly, providing microscopic insight into the origin of the enantiosorption in the framework.

Full text of DOI:10.1021/acs.inorgchem.8b00948

Communication
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Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Enantioselective Separation over a Chiral Biphenol-Based Metal−
Organic Framework
Anees Abbas,† Zhao-Xi Wang,†,‡ Zijian Li,† Hong Jiang,† Yan Liu,*,† and Yong Cui*,†
†School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong
University, Shanghai 200240, China
‡Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, Innovative Drug Research Center, Shanghai
University, Shanghai 200444, China
S
* Supporting Information
carboxylate bridging ligand and Cd2+, and the enantioseparation
ABSTRACT: A chiral porous 3D metal−organic frame-
work (MOF) is constructed from an enantiopure
carboxylate ligand of 1,1′-biphenol, which can be utilized
as adsorbent for the separation of aromatic alcohols and
sulfoxides with enantioselectivity of up to 99.4%. Single-
crystal X-ray diffraction analysis reveals the binding sites
and host−guest interactions clearly, providing microscopic
insight into the origin of the enantiosorption in the
framework.
property toward aromatic alcohols and sulfoxides. An
investigation of host−guest complex by single-crystal X-ray
diffraction technique is conducted to give a straightforward
insight and deeper understanding of enantioselective discrim-
ination.
The tetracarboxylate bridging ligand H4L was synthesized by
bromination of (S)-6,6′-dimethyl-5,5′-di(3,5-bis-
(methoxycarbonyl)phenyl-1,1′-biphenyl-2,2-diol followed by
LiOH catalyzed hydrolysis in 78% overall yield. H4L was
1
characterized by H and 13C NMR spectroscopy (Figure S1)
and ESI-MS (Figure S2). A mixture of H4L and Cd(NO3)2·
4H2O (in a 1:6 molar ratio) in DMF and CH3CN was heated at
he preparation of chiral compounds in enantiomerically
Tpure form is extremely important in fine chemical and 100 °C for 12 h to yield colorless crystals in 80% yield. Based on
single-crystal X-ray diffraction (XRD), elemental analysis, and
thermogravimetric analysis (TGA), the crystal was formulated
as [Cd2L(DMF)2(H2O)]·DMF·3H2O (1).
pharmaceutical industries, also a challenging goal in modern
organic synthesis.1 Chiral separation is efficient for achieving
enantiopure chiral molecules.2,3 However, it is perceived as
expensive and inefficient for the production of undesired
enantiomer, and chiral selectors with low cost and superior
capacity are still rather rare.3 Crystalline porous metal−organic
frameworks (MOFs) have emerged as an ideal scaffold to
construct the separation materials, whose highly tunable
structures can be precisely tailored for adsorption of specific
molecules.4 A sensible and discrete incorporation of multiple
chiral recognition sites into MOFs can incisively control the
orientation of two enantiomers within the confined micro-
environment to boost enantiospecific interactions, thus exerting
efficient stereocontrol and enantiomeric recognition.5 The
separation of enantiomers with chiral MOFs via crystallization,
chromatography, and membrane has been reported, and good
results have been achieved in the separation of small alcohols,
amines, amino acids, sulfoxides, and so on.6 Nevertheless, the
resolution of racemic molecules is only evaluated for a relative
small number of components with similar properties, and the
development of novel MOF-based separators capable of
furnishing wider separation ability is still an important and
challenging task.
Single-crystal XRD study shows that 1 crystallizes in the chiral
orthorhombic P212121 space group with one whole formula in
the asymmetric unit. There are two crystallographically
independent Cd(II) atoms in the structure. Cd1 is octahedrally
coordinated by six carboxylate oxygen atoms of four L ligands,
whereas Cd2 coordinates to three carboxylate oxygen atoms of
three ligands and one water and two DMF molecules, with Cd−
O bond lengths ranging from 2.205(4) to 2.380(4) Å. Cd1 and
Cd2 are bridged by one μ2−η1,η2 and two μ2−η1,η1 carboxylate
groups with Cd1 also coordinated by a chelating carboxylate
group and Cd2 coordinated by solvents to form a Cd2(CO2)4
cluster. Each L ligand adopts an exo-heptadentate coordination
fashion to bridge seven Cd ions of four Cd2 clusters via four
bidentate carboxylate groups. Adjacent dicadmium units are
linked through bridging carboxylate groups to form 21 helical
chains, which are further connected by the L linkers to generate a
3D framework with 1D channels of ∼0.65 × 1.16 nm2 along the
a-axis. If the ligand L and Cd2 cluster are both viewed as 4-
connecting nodes, the final 3D network can be simplified as a 4-c
2
3
̈
net of sra topology with the point (Schlafli) symbol (4 ·6 ·8)
(Figure 1).
Chiral 1,1′-biphenol, a powerful organic backbone for
asymmetric induction,7 has been immobilized into structurally
porous frameworks for the highly enantioselective separation.8
For instance, chiral Dy−Na−biphenol framework has been
explored as adsorbent for separation of mandelate derivatives,8a
while Mn−biphenol architecture can resolve racemic aromatic
and aliphatic amines.6d In this work, we present the synthesis of a
chiral porous MOF constructed from 1,1′-biphenol-derived
PLATON calculation shows that 1 contains about 47.5% void
space available for guest inclusion.9 TGA showed that the guest
molecules could be removed in 50−300 °C. An additional
weight loss of around 13% occurring at higher temperatures
Received: April 9, 2018
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.8b00948
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
Communication
meric excess (ee) with the R-enantiomer being in excess. The
enantiosorption kinetics was studied by 1H NMR monitoring at
different times. As shown in Figure 2, the adsorption of 1 to 1-
Figure 2. Adsorption kinetic profile of (S)-1 toward 1-phenylethanol.
phenylethanol reached equilibrium in 6 h, and the expected
formation of kinetically stable 1:1 host−guest complex was also
observed by 1H NMR spectroscopy.
We then examined different aromatic alcohols under the
optimized conditions to evaluate the enantioseparation
capability of 1 (Table 1). Various alcohols with electron-
Table 1. Enantiosorption of (S)-1 Towards Racemic Alcohols
a
and Sulfoxides
Figure 1. (a) Construction of MOF 1 from H4L and dimeric
[Cd2(CO2)4(DMF)2(H2O)]. (b) The sra topology of 1. (c) The 3D
porous structure of 1 viewed along the a-axis (Cd, light green
polyhedral; C, gray; O, red; N, light blue; Br, orange; H atoms are
omitted for clarity).
(300−400 °C) may be due to the loss of one coordinated water
and two coordinated DMF molecules (Figure S3). The phase
purity of bulk sample of 1 was established by comparison of its
observed and simulated PXRD patterns, though the loss of guest
molecules during the test may lead to a little distortion of the
framework (Figure S4). The solid-state circular dichroism (CD)
spectra of 1 based on the opposite enantiomers of H4L are
mirror images of each other, suggesting their enantiomeric
nature (Figure S5). The scanning electron microscopy (SEM)
image of 1 revealed the formation of rod-like particles with a
wide range of sizes in micrometer level (Figure S6). N2
adsorption measurement showed only surface adsorption,
probably due to incomplete removal of solvent molecules in
the pores as a result of strong host−guest hydrogen-bonding
interactions, and/or possible structural distortions upon
activation. Compound 1 could adsorb ∼1.4 Rhodamine 6G
per formula unit in solution, demonstrating its porous nature
and structural integrity in solution.
The chiral porous structure and available chiral dihydroxyl
groups of 1 have enabled us to examine its potential for
enantioselective separation. The performance was first evaluated
by enantioseparation of 1-phenylethanol. After initial optimiza-
tion of the conditions by screening different solvents and
temperatures, the inclusion was achieved by cocrystallization of
evacuated (S)-1 and 1-phenylethanol in DCM at room
temperature. The released alcohol, obtained by soaking the
inclusion solids in Et2O was analyzed by chiral high-perform-
ance liquid chromatography (HPLC), yielding 99% enantio-
a
For details see the experimental section in Supporting Information.
Determined by HPLC (letters in brackets specify the preferable
b
isomer).
withdrawing substituents in the aromatic ring could be
successfully separated, with 93%, 98%, and 98% ee values for
1-(4-fluorophenyl)ethanol, 1-(4-chlorophenyl)ethanol, and 1-
(4-bromophenyl)ethanol, respectively. When the methyl group
of 1-phenylethanol was replaced by ethyl group, the substrate 1-
phenylpropanol was resolved with 92% enantioselectivity. The
highest sorption ee value observed for alcohols studied was
99.4% for 1-(1-naphthyl)ethanol. These results clearly showed
that 1 represents one of the best framework adsorbents for the
separation of racemic alcohols reported to date.8b,10
Chiral sulfoxides constitute an important class of biologically
active compounds and therapeutic drugs.11 Compound 1 also
showed remarkable resolution capability toward sulfoxides.
B
DOI: 10.1021/acs.inorgchem.8b00948
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Inorganic Chemistry
Communication
Methyl phenyl sulfoxide, ethyl phenyl sulfoxide, 3-methox-
yphenyl methyl sulfoxide, and 4-methoxyphenyl methyl
sulfoxide were efficiently resolved by the apohost 1 with
enantioselectivity ranging from 80 to 96%. Lansoprazole, a
pharmacologically important proton pump inhibitor (PPI),12
could be separated with 91% enantioselectivity. Chiral MOFs
have been developed for enantioseparation of sulfoxides,5f,13 and
the highest ee reported prior to this work was 62%.13c
Importantly, the present MOF represents a new generation of
chiral solid separator, which is capable of enantioseparation of
racemic alcohols and sulfoxides.
It is notable that ligand H4L alone cannot resolve the
enantiomers of alcohol and sulfoxide under identical conditions.
Furthermore, the adsorbent 1 could be recovered easily through
centrifugation and reactivated by ultrasonic washing with DCM
for several times. The reactivated material was reused directly in
the subsequent run, and the enantioselectivity did not decrease
obviously after three cycles. The high angle data of the PXRD
pattern gets broader, which is indicative of partial framework
collapse.
To investigate the nature of enantioselectivity as well as the
characteristics of the interactions between host framework and
adsorbate molecules, the structure of host−guest complex was
carefully examined. Single crystals of 1·4-BrPhEtOH (4-
BrPhEtOH = 1-(4-bromophenyl)ethanol) were synthesized
through the same procedure as that used for 1, except that
additional 4-BrPhEtOH and MeOH were added. The structure
clearly revealed that the adduct 1·4-BrPhEtOH is isostructural
to the original host structure (Figure 3a). Only (S)-4-
benzene ring of the ligand (C···O = 3.173 and 2.919 Å). The
methyl group of alcohol interacts with the chiral OH group of
the biphenol backbone through the bridge of free water guests to
form C−H···O interaction and hydrogen bonds (C···O = 2.200
Å; O···O = 2.321 and 2.684 Å) and forms C−H···O interaction
(C···O = 2.988 Å) with the carboxyl oxygen atom. The structure
is further reinforced by face-to-face intermolecular π−π
interaction: each 4-BrPhEtOH unit is engaged in one π−π
stacking (plane-to-plane separation = 3.868 Å and dihedral angle
= 26°) with one benzene ring of the ligand. In addition, the weak
C−H···Br interaction formed between the Br atom of 4-
BrPhEtOH with the coordinated DMF (C···Br = 3.399 Å) may
also have some impact on the enantioselective recognition
process. Therefore, the multiple supramolecular interactions
between host and guest molecule within the chiral micro-
environment thus provide the key driving force and may be
responsible for the efficient recognition and separation.
In summary, we have presented the assembly of a chiral
porous MOF from enantiopure tetracarboxylic acid-function-
alized 1,1′-biphenol ligand. The framework can serve as an
efficient solid adsorbent for the separation of racemic aromatic
alcohols and sulfoxides. Remarkably, crystallographically
observed host−guest interactions elucidated the nature of
enantioselective recognition and separation. Further research
endeavors on resolving other racemic molecules and exploration
of MOF-based adsorbents for practical useful enantioseparation
processes are underway.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.8b00948.
Experimental details, crystallographic data, and spectral
data (PDF)
Accession Codes
CCDC 1835511−1835512 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge via www.ccdc.cam.ac.uk/data_request/cif, or by email-
ing data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: liuy@sjtu.edu.cn.
*E-mail: yongcui@sjtu.edu.cn.
ORCID
Zhao-Xi Wang: 0000-0002-2689-7034
Yan Liu: 0000-0002-7560-519X
Yong Cui: 0000-0003-1977-0470
Figure 3. (a) View of the structure of host−guest complex 1·4-
BrPhEtOH. (b) Scheme showing the multiple intermolecular
interactions between (S)-1 and (S)-4-BrPhEtOH.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
BrPhEtOH was observed in (S)-1, which is consistent with
the separation experiment. Each of the trapped alcohols is
involved with different supramolecular interactions (Figure 3b).
The OH group of alcohol interacts with adjacent carboxylate
oxygen to form a hydrogen bond (O···O = 2.401 Å) and forms
C−H···O interactions with the coordinated DMF and the
This work was supported by the National Natural Science
Foundation of China (21431004, 21522104, and
21620102001), the National Key Basic Research Program of
China (2014CB932102 and 2016YFA0203400), Key Project of
Basic Research of Shanghai (17JC1403100 and 18JC1413200),
and the Shanghai “Eastern Scholar” Program.
C
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