A Bumper Crop of Boiling-Water-Stable Metal-Organic Frameworks from Controlled Linker Sulfuration

Article abstract of DOI:10.1021/acs.inorgchem.0c00576

The series of highly stable porous solids here feature systematic, regiospecific sulfur substitutions on the organic linkers for versatile functions. One major surprise lies in the controllable sequential reactions between sodium thiomethoxide (NaSMe) and octafluorobiphenyl-4,4′-dicarboxylic acid (H₂bpdc-8F; this was readily made without precious metal catalysts). Namely, 3, 4, 6, and 8 methylthio-substitutions can be respectively achieved with regiospecificity (i.e., to produce the four molecules H₂bpdc-3S5F, H₂bpdc-4S4F, H₂bpdc-6S2F, H₂bpdc-8MS). A second surprise lies in their persistent formation of the UiO-67-type net with Zr(IV) ions, e.g., even in the case of the fully sulfurated H₂bpdc-8MS. In addition to the remarkable breadth of functional control, all the Zr(IV)-based crystalline solids here are stable in boiling water (e.g., for 24 h) and in air as solventless, activated porous solids. Moreover, the thioether groups allow for convenient H₂O₂ oxidation to fine-tune the hydrophilicity and luminescence properties and improve proton conductivity.

Full text of DOI:10.1021/acs.inorgchem.0c00576

pubs.acs.org/IC
Article
A Bumper Crop of Boiling-Water-Stable Metal−Organic Frameworks
from Controlled Linker Sulfuration
Wan-Ru Xian,§ Yonghe He,§ Yingxue Diao, Yan-Lung Wong, Hua-Qun Zhou, Sai-Li Zheng,
Wei-Ming Liao, Zhengtao Xu,* and Jun He*
Cite This: https://dx.doi.org/10.1021/acs.inorgchem.0c00576
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: The series of highly stable porous solids here
feature systematic, regiospecific sulfur substitutions on the organic
linkers for versatile functions. One major surprise lies in the
controllable sequential reactions between sodium thiomethoxide
(NaSMe) and octafluorobiphenyl-4,4′-dicarboxylic acid (H2bpdc-
8F; this was readily made without precious metal catalysts).
Namely, 3, 4, 6, and 8 methylthio-substitutions can be respectively
achieved with regiospecificity (i.e., to produce the four molecules
H2bpdc-3S5F, H2bpdc-4S4F, H2bpdc-6S2F, H2bpdc-8MS). A
second surprise lies in their persistent formation of the UiO-67-
type net with Zr(IV) ions, e.g., even in the case of the fully
sulfurated H2bpdc-8MS. In addition to the remarkable breadth of
functional control, all the Zr(IV)-based crystalline solids here are stable in boiling water (e.g., for 24 h) and in air as solventless,
activated porous solids. Moreover, the thioether groups allow for convenient H2O2 oxidation to fine-tune the hydrophilicity and
luminescence properties and improve proton conductivity.
ariable pore size, variable chemical functionality, and
reactivity in the crystalline medium remain major
V
incentives in the pursuit of the diverse solids of metal−organic
frameworks (MOFs).1−12 The modular nature of MOF
structures was highlighted in the earlier silver-nitrile1,13−17
and Zn(II)-carboxylate networks2 as well as the currently
thriving Zr(IV)-based system initiated by Lillerude.18−23 In
these studies, the size and shape of the linker backbone are
systematically varied to effectively impact the net topology and
pore features.24−29 On the other hand, the attachment of
secondary groups (e.g., side chains) opens up intriguing
horizons for novel functions and properties in the well-defined
porous medium of MOF crystals.30−35 Besides topical areas
such as catalysis36−43 and environmental remediation,44−49
side chain groups, by sheer volume, occupy the void space so
as to fine-tune the microporous features. To optimize the
performances of MOF solids, it is desirable to develop versatile
linker systems that can be conveniently modified in the
number and function of the secondary groups.
Figure 1. Molecule H2bpdc-8F and its methylthio derivatives H2bpdc-
3S5F, H2bpdc-4S4F, H2bpdc-6S2F, H2bpdc-8MS, and the known
H2TMBPD.
Just such a system is described here. Building on our
longstanding effort in utilizing thiolate anions as facile
nucleophiles for accessing functional building blocks for
framework materials,50−54 we set eyes on the perfluoronated
substrate H2bpdc-8F (octafluorobiphenyl-4,4′-dicarboxylic
acid; Figure 1): this molecule was earlier made by Miljanic
et al.,55 but Larionov et al. subsequently reported an easier
synthesis56 entailing no expensive transition metal catalysts. As
an initial test, we subjected the dimethyl ester of H2bpdc-8F to
Received: February 22, 2020
https://dx.doi.org/10.1021/acs.inorgchem.0c00576
© XXXX American Chemical Society
Inorg. Chem. XXXX, XXX, XXX−XXX
A

Inorganic Chemistry
pubs.acs.org/IC
Article
the simple sulfur nucleophile methylthiolate (Figure S1).
Surprisingly, the displacement of the fluoro groups by the
sulfur groups follows a controllable sequence that allows easy
isolation of each of the four isomers as shown in Figure 1 (i.e.,
the tri-, tetra-, hexa-, and octa-substituted products of H2bpdc-
3S5F, H2bpdc-4S4F, H2bpdc-6S2F, and H2bpdc-8MS).
Because of the increasing importance of the versatile sulfur
groups for functionalizing the MOF host,30 we are motivated
to communicate this synthetic discovery together with the
series of MOF products that also stand out for their remarkable
stability in water and air.
products were revealed in the powder X-ray diffraction
(PXRD) patterns (Figure 3). Among these, single crystals
H2bpdc-8F was synthesized using the inexpensive reagents
of SnCl2, zinc powder, and CuCl2 in gram scale with no need
for chromatographic separation, while the degree of sulfuration
can be controlled by the reactants H2bpdc-8F/MeSNa ratio
and reaction time to systematically target each of the four
products (H2bpdc-3S5F, H2bpdc-4S4F, H2bpdc-6S2F, and
H2bpdc-8MS) as linkers for MOF assembly. The character-
ization of the linker products includes solution 1H, 19F and 13
C
NMR as well as single-crystal X-ray diffraction (SCXRD)
studies. For example, the SCXRD structures of the MOF
crystals of Pb-bpdc-4S4F and Pb-bpdc-8MS (obtained by
solvothermally reacting in CH3CN/H2O mixed solvents
Pb(NO3)2 with H2bpdc-4S4F and H2bpdc-8MS, respectively)
unambiguously reveals the eight MeS substituents of bpdc-
8MS land the para-substitutions of bpdc-4S4F (Figures S37
and S38). Notice that Pb-bpdc-4S4F adopts the chiral space
group P212121 due to the axial chirality of the biaryl linker
bpdc-4S4F. The main focus is, however, presently on the
Zr(IV)-based MOF products because of the distinct
modularity (i.e., consistently adopting the UiO-67-type
network; Figure 2) and the remarkable framework stability
achieved.
Figure 3. Powder X-ray diffraction patterns (Cu Kα, λ = 1.5418 Å) of
(a) a simulation from the single crystal structure of Zr-bpdc-4S4F
(single crystal data collected at 100 K); (b, e, h, k) the as-made
samples of Zr-bpdc-3S5F, Zr-bpdc-4S4F, Zr-bpdc-6S2F, and Zr-bpdc-
8MS, respectively; (c, f, i, l) the activated samples (Soxhlet extraction
with methanol for 3 days) of Zr-bpdc-3S5F, Zr-bpdc-4S4F, Zr-bpdc-
6S2F, and Zr-bpdc-8MS, respectively; (d, g, j, m) the boiling-water-
treated sample of Zr-bpdc-3S5F, Zr-bpdc-4S4F, Zr-bpdc-6S2F, and
Zr-bpdc-8MS, respectively.
Crystalline solids of Zr-bpdc-3S5F, Zr-bpdc-4S4F, and Zr-
bpdc-6S2F were obtained by solvothermally reacting (in DMF
solvent) ZrCl4 with H2bpdc-3S5F, H2bpdc-4S4F, and H2bpdc-
6S2F, respectively. The phase-pure, UiO-67-type MOF
suitable for X-ray studies were obtained for Zr-bpdc-4S4F,
which unveils its isoreticular relation to the UiO-67 prototype
(i.e., Zr-BPD with fcc-arrayed Zr6O8 units18) but with well-
defined sulfur and fluoro functions (Figure 2). Elemental
results on the activated samples (e.g., from Soxhlet extraction
in methanol) can be fitted with the formulas of
Zr6O4(OH)4(bpdc-3S5F)5.1(HCOO)1.8(H2O)2 for Zr-bpdc-
3S5F, Zr6O4(OH)4(bpdc-4S4F)4(HCOO)4(H2O)3 for Zr-
bpdc-4S4F, Zr6O4(OH)4(bpdc-6S2F)3.4(HCOO)5.2 for Zr-
b p d c - 6 S 2 F , a n d Z r
O ( O H ) ( b p d c -
6
4 4
8MS)3.2(HCOO)5.6(CH3OH)9.5 for Zr-bpdc-8MS. The greater
ligand deficiency observed in Zr-bpdc-8MS can be attributed
to the bulkiness of the fully sulfurated bpdc-8MS linker (i.e., it
is sterically more demanding to fit this linker around the Zr−O
cluster).
The stability of the MOF materials is also demonstrated by
both PXRD and gas sorption studies. The activated samples of
Zr-bpdc-3S5F, Zr-bpdc-4S4F, Zr-bpdc-6S2F, and Zr-bpdc-
8MS all exhibit long-term stability, e.g., without significant
broadening of the PXRD peaks, when exposed to air in the
absence of solvents (Figure 3, patterns c, f, i, l). The N2
sorption isotherms (77 K) feature dominant type-I character-
istics of microporous solids (Figure 4, panels a, c, e, g). The
BET surface areas are calculated to be 986 m2·g−1 for Zr-bpdc-
3S5F, 835 m2·g−1 for Zr-bpdc-4S4F, 657 m2·g−1 for Zr-bpdc-
6S2F, and 449 m2·g−1 for Zr-bpdc-8MS (see also Table S1).
Figure 2. An octahedral cage from the single crystal structure of the
Zr-bpdc-4S4F framework. The disorder of the linker molecule is not
shown. Zr coordination polyhedra are displayed in cyan. Atom colors:
red, O; yellow, S; gray, C; blue, F.
B
https://dx.doi.org/10.1021/acs.inorgchem.0c00576
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
crystalline phases (Figure 3, patterns d, g, j, m). Moreover, gas
sorption studies indicate that the boiling-water-treated samples
continue to feature type-I isotherms characteristic of micro-
porous solids (Figure 4, panels b, d, f, h), with the surface areas
largely maintained compared with before boiling water
treatment (e.g., <10% variation in surface areas): 936 m2·g−1
for Zr-bpdc-3S5F, 779 m2·g−1 for Zr-bpdc-4S4F, 648 m2·g−1
for Zr-bpdc-6S2F, and 335 m2·g−1 for Zr-bpdc-8MS.
Compared with more fragile unsubstituted UiO-67 solid
(e.g., crystallinity degrading upon solvent removal),58−60 the
air and water stability of this series of Zr-MOF solids, together
with the recent example of ZrTMBPD, with TMBPD being
3,3′,5,5′-tetrakis(methylthio)biphenyl dicarboxylate (Figure
1),54 demonstrate the usefulness of sulfur functions (e.g., by
means of their steric shield around the metal cluster) for
accessing stable MOF materials.
Postsynthetic oxidation of the Zr-bpdc-4S4F crystals is also
informative. With the vigorous oxidizer of 30% H2O2, all four
thioether groups of the linker were converted into the sulfone
1
functions (as verified by the IR, H and 19F NMR spectra;
Figures S40−S42), without compromising the framework
lattice (e.g., PXRD in Figure S43). By comparison, thorough
conversion into sulfone was not feasible in ZrTMBPD: i.e.,
treatment by 5% H2O2 led to a sulfone/sulfoxide mixture,
while more stringent oxidation (e.g., by 30% H2O2) degraded
the framework. The steric factor is obvious: in ZrTMBPD, all
the S groups are crowded around the Zr6 cluster, leaving less
room for the incoming O atoms; while such crowding is
lessened in Zr-bpdc-4S4F by the smaller F atoms ortho to the
carboxyl donors.
The sulfone-equipped crystal (denoted as Zr-bpdc-
4SO2Me4F) features greatly increased hydrophilicity with a
water contact angle of 64°, relative to 91° for Zr-bpdc-4S4F
(Figure S44). The enhanced hydrophilicity is also consistent
with the higher proton conductivities of Zr-bpdc-4SO2Me4F
(Figure S45), e.g., about 1.75 × 10−4 S·cm−1 at 80 °C and 90%
relative humidity (pellet sample), representing a thousand-fold
increase from the sulfide precursor Zr-bpdc-4S4F (Figures S46
and S47). The fluorescence of the H2O2 oxidation process is
monitored to reveal an interesting dynamic (Figure 5). The Zr-
bpdc-4S4F solid features blue fluorescence in moderate
intensity with λmax = 430 nm (λex = 360 nm); the intensity
initially goes down (λmax little changed), reaching a minimum
Figure 4. N2 sorption isotherms at 77 K and BET plot (insets) for the
activated MOFs: (a) Zr-bpdc-3S5F, (c) Zr-bpdc-4S4F, (e) Zr-bpdc-
6S2F, and (g) Zr-bpdc-8MS and the boiling-water-treated samples of
(b) Zr-bpdc-3S5F, (d) Zr-bpdc-4S4F, (f) Zr-bpdc-6S2F, and (h) Zr-
bpdc-8MS.
The steadily decreasing surface areas in this series are
consistent with the increasing degree of sulfuration and the
resultant bulkiness of the linkers taking up more of the pore
space. This trend also fits with the measured surface area and
pore volume (SBET = 1877 m2/g and Vmicro = 0.85 cm3 g−1) for
the unsubstituted UiO-67 prototype.57
The MOF samples were also found to be remarkably stable
to aqueous environments. For example, even after being boiled
in water (100 °C) for 24 h, the PXRD peaks of all four samples
remain sharp and strong, being consistent with the native
Figure 5. (a) Room temperature emission spectra (λex = 360 nm) and (b) the bar graph of intensity against reaction time for Zr-bpdc-4S4F reacted
with 30% H2O2 (insets: photographs of the solid samples under 360 nm radiation).
C
https://dx.doi.org/10.1021/acs.inorgchem.0c00576
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
(about 1/3 of the original) at 1.0 h of reaction time, after
which the trend reverses to plateau (after 3 days) at twice the
intensity of Zr-bpdc-4S4F, with λmax also red-shifted (to about
450 nm) to feature the distinct green emission of Zr-bpdc-
4SO2Me4F. The original emission possibly arises from the
coupling of the sulfide S donors and the electron-accepting
biphenyl/carboxyl moieties; the initial oxidation of S (e.g., into
sulfoxide) diminishes its donor character, thus weakening the
luminescence. Further oxidation, however, generates multiple
electropositive sulfone groups (e.g., to couple with the fluoro
lone-pair electrons), which expand the conjugate system to
red-shift the emission and rigidify the linker backbone for
stronger luminescence.
Taken together, the significant synthetic progresses here
broadly span three areas: (1) targeted linker molecule synthesis
with precise control on the thioether numbers and positions
installed; (2) modular, persistent formation of the prototype
(UiO-67) porous frameworks stable to boiling water and air;
(3) diverse postsynthetic modifications as illustrated by the
tunable oxidation of the sulfide groups (all the way into the
sulfone groups). Further exploration of the facile substitution
of the −F groups (e.g., by conjugated or chiral nucleophiles) is
warranted by the functional versatility of this platform of
porous solid synthesis based on polyfluoronated aromatic
substrates.
Hua-Qun Zhou − School of Chemical Engineering and Light
Industry, Guangdong University of Technology, Guangzhou
510006, Guangdong, China
Sai-Li Zheng − School of Chemical Engineering and Light
Industry, Guangdong University of Technology, Guangzhou
510006, Guangdong, China
Wei-Ming Liao − School of Chemical Engineering and Light
Industry, Guangdong University of Technology, Guangzhou
510006, Guangdong, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.0c00576
Author Contributions
§W.R.X. and Y.H. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was funded by the Local Innovative and Research
Teams Project of Guangdong Pearl River Talents Program
(2017BT01Z032), National Natural Science Foundation of
China (21871061, 21901046), and Science and Technology
Planning Project of Guangdong Province (2017A050506051),
Science and Technology Program of Guangzhou
(201807010026). Z.X. acknowledges an ARG (CityU
9667168) grant.
ASSOCIATED CONTENT
■
sı
* Supporting Information
REFERENCES
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.0c00576.
■
(1) Kiang, Y.-H.; Gardner, G. B.; Lee, S.; Xu, Z.; Lobkovsky, E. B.
Variable Pore Size, Variable Chemical Functionality, and an Example
of Reactivity within Porous Phenylacetylene Silver Salts. J. Am. Chem.
Soc. 1999, 121, 8204−8215.
General synthetic experimental details, NMR spectra,
and IR, PXRD, TGA, CHN, and BET results (PDF)
(2) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.;
O’Keeffe, M.; Yaghi, O. M. Systematic design of pore size and
functionality in isoreticular MOFs and their application in methane
storage. Science 2002, 295, 469−472.
Accession Codes
CCDC 1985579−1985581 contain the supplementary crys-
tallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by
emailing data_request@ccdc.cam.ac.uk, or by contacting The
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(3) Cohen, S. M. The Postsynthetic Renaissance in Porous Solids. J.
Am. Chem. Soc. 2017, 139, 2855−2863.
(4) Ali Akbar Razavi, S.; Morsali, A. Linker functionalized metal-
organic frameworks. Coord. Chem. Rev. 2019, 399, 213023.
(5) Hoskins, B. F.; Robson, R. Infinite polymeric frameworks
consisting of three dimensionally linked rod-like segments. J. Am.
Chem. Soc. 1989, 111, 5962−5964.
(6) Kondo, M.; Yoshitomi, T.; Seki, K.; Matsuzaka, H.; Kitagawa, S.
Three-dimensional framework with channeling cavities for small
molecules: {[M2(4,4′-bpy)3(NO3)4].xH2O}n (M = Co, Ni, Zn).
Angew. Chem., Int. Ed. Engl. 1997, 36, 1725−1727.
(7) MacGillivray, L. R.; Subramanian, S.; Zaworotko, M. J.
Interwoven two- and three-dimensional coordination polymers
through self-assembly of CuI cations with linear bidentate ligands. J.
Chem. Soc., Chem. Commun. 1994, 1325−1326.
(8) Gardner, G. B.; Venkataraman, D.; Moore, J. S.; Lee, S.
Spontaneous assembly of a hinged coordination network. Nature
1995, 374, 792−795.
AUTHOR INFORMATION
■
Corresponding Authors
Jun He − School of Chemical Engineering and Light Industry,
Guangdong University of Technology, Guangzhou 510006,
Guangdong, China; orcid.org/0000-0001-7062-4001;
Email: junhe@gdut.edu.cn
Zhengtao Xu − Department of Chemistry, City University of
Hong Kong, Kowloon, Hong Kong, China; orcid.org/0000-
0002-7408-4951; Email: zhengtao@cityu.edu.hk
Authors
(9) Chui, S. S. Y.; Lo, S. M. F.; Charmant, J. P. H.; Orpen, A. G.;
Williams, I. D. A chemically functionalizable nanoporous material
[Cu3(TMA)2(H2O)3]n. Science 1999, 283, 1148−1150.
(10) Yaghi, O. M.; Li, G. M.; Li, H. L. Selective Binding and
Removal of Guests in a Microporous Metal-Organic Framework.
Nature 1995, 378, 703−706.
Wan-Ru Xian − School of Chemical Engineering and Light
Industry, Guangdong University of Technology, Guangzhou
510006, Guangdong, China
Yonghe He − School of Chemical Engineering and Light
Industry, Guangdong University of Technology, Guangzhou
510006, Guangdong, China
Yingxue Diao − Department of Chemistry, City University of
Hong Kong, Kowloon, Hong Kong, China
Yan-Lung Wong − Department of Chemistry, City University of
Hong Kong, Kowloon, Hong Kong, China
(11) Huang, X.; Zhang, J.; Chen, X. [Zn(bim)2]·(H2O)1.67: a
metal-organic open-framework with sodalite topology. Chin. Sci. Bull.
2003, 48, 1531−1534.
(12) Gai, Y.; Chen, X.; Yang, H.; Wang, Y.; Bu, X.; Feng, P. A new
strategy for constructing a disulfide-functionalized ZIF-8 analogue
D
https://dx.doi.org/10.1021/acs.inorgchem.0c00576
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
using structure-directing ligand-ligand covalent interaction. Chem.
Commun. 2018, 54, 12109−12112.
(13) Choe, W.; Kiang, Y. H.; Xu, Z.; Lee, S. Coordination Networks
of C3v and C2v Phenylacetylene Nitriles and Silver(I) Salts: Interplay
of Ligand Symmetry and Molecular Dipole Moments in the Solid
State. Chem. Mater. 1999, 11, 1776−1783.
(14) Xu, Z.; Lee, S.; Kiang, Y.-H.; Mallik, A. B.; Tsomaia, N.;
Mueller, K. T. A cross-linked large channel organic coordination solid.
Adv. Mater. 2001, 13, 637−641.
(15) Xu, Z.; Kiang, Y.-H.; Lee, S.; Lobkovsky, E. B.; Emmott, N.
Hydrophilic-to-hydrophobic volume ratios as structural determinant
in small-length scale amphiphilic crystalline systems: silver salts of
phenylacetylene nitriles with pendant oligo(ethylene oxide) chains. J.
Am. Chem. Soc. 2000, 122, 8376−8391.
(16) Kiang, Y.-H.; Gardner, G. B.; Lee, S.; Xu, Z. Porous Siloxane
Linked Phenylacetylene Nitrile Silver Salts from Solid State
Dimerization and Low Polymerization. J. Am. Chem. Soc. 2000, 122,
6871−6883.
(17) Kiang, Y. H.; Lee, S.; Xu, Z.; Choe, W.; Gardner, G. B.
Persistent honeycomb structures in porous and other two-component
solids. Adv. Mater. 2000, 12, 767−770.
(18) Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti,
C.; Bordiga, S.; Lillerud, K. P. A New Zirconium Inorganic Building
Brick Forming Metal Organic Frameworks with Exceptional Stability.
J. Am. Chem. Soc. 2008, 130, 13850−13851.
(19) Zhang, Y.; Zhang, X.; Lyu, J.; Otake, K.-i.; Wang, X.; Redfern,
L. R.; Malliakas, C. D.; Li, Z.; Islamoglu, T.; Wang, B.; Farha, O. K. A
Flexible Metal-Organic Framework with 4-Connected Zr6 Nodes. J.
Am. Chem. Soc. 2018, 140, 11179−11183.
(20) Pang, J.; Yuan, S.; Qin, J.; Liu, C.; Lollar, C.; Wu, M.; Yuan, D.;
Zhou, H. C.; Hong, M. Control the Structure of Zr-Tetracarboxylate
Frameworks through Steric Tuning. J. Am. Chem. Soc. 2017, 139,
16939−16945.
(21) Yang, P.; Shu, Y.; Zhuang, Q.; Li, Y.; Gu, J. A robust MOF-
based trap with high-density active alkyl thiol for the super-efficient
capture of mercury. Chem. Commun. 2019, 55, 12972−12975.
(22) Rimoldi, M.; Howarth, A. J.; DeStefano, M. R.; Lin, L.;
Goswami, S.; Li, P.; Hupp, J. T.; Farha, O. K. Catalytic Zirconium/
Hafnium-Based Metal-Organic Frameworks. ACS Catal. 2017, 7,
997−1014.
(23) Yuan, S.; Qin, J.-S.; Lollar, C. T.; Zhou, H.-C. Stable Metal-
Organic Frameworks with Group 4 Metals: Current Status and
Trends. ACS Cent. Sci. 2018, 4, 440−450.
(24) Zhang, X.; Zhang, X.; Johnson, J. A.; Chen, Y.-S.; Zhang, J.
Highly Porous Zirconium Metal-Organic Frameworks with β-UH3-
like Topology Based on Elongated Tetrahedral Linkers. J. Am. Chem.
Soc. 2016, 138, 8380−8383.
(25) Ye, Y.; Zhao, L.; Hu, S.; Liang, A.; Li, Y.; Zhuang, Q.; Tao, G.;
Gu, J. Specific detection of hypochlorite based on the size-selective
effect of luminophore integrated MOF-801 synthesized by a one-pot
strategy. Dalton Trans. 2019, 48, 2617−2625.
(31) Li, B.; Chrzanowski, M.; Zhang, Y.; Ma, S. Applications of
metal-organic frameworks featuring multi-functional sites. Coord.
Chem. Rev. 2016, 307, 106−129.
(32) He, J.; Zeller, M.; Hunter, A. D.; Xu, Z. Functional shakeup of
metal-organic frameworks: the rise of the sidekick. CrystEngComm
2015, 17, 9254−9263.
(33) Lee, J.; Lim, D.-W.; Dekura, S.; Kitagawa, H.; Choe, W. MOP
× MOF: Collaborative Combination of Metal-Organic Polyhedra and
Metal-Organic Framework for Proton Conductivity. ACS Appl. Mater.
Interfaces 2019, 11, 12639−12646.
(34) Nam, D.; Huh, J.; Lee, J.; Kwak, J. H.; Jeong, H. Y.; Choi, K.;
Choe, W. Cross-linking Zr-based metal-organic polyhedra via
postsynthetic polymerization. Chem. Sci. 2017, 8, 7765−7771.
(35) Chen, T.-F.; Han, S.-Y.; Wang, Z.-P.; Gao, H.; Wang, L.-Y.;
Deng, Y.-H.; Wan, C.-Q.; Tian, Y.; Wang, Q.; Wang, G.; Li, G.-S.
Modified UiO-66 frameworks with methylthio, thiol and sulfonic acid
function groups: The structure and visible-light-driven photocatalytic
property study. Appl. Catal., B 2019, 259, 118047.
(36) Wu, X.; Han, X.; Xu, Q.; Liu, Y.; Yuan, C.; Yang, S.; Liu, Y.;
Jiang, J.; Cui, Y. Chiral BINOL-Based Covalent Organic Frameworks
for Enantioselective Sensing. J. Am. Chem. Soc. 2019, 141, 7081−
7089.
(37) Xia, Q.; Li, Z.; Tan, C.; Liu, Y.; Gong, W.; Cui, Y. Multivariate
Metal-Organic Frameworks as Multifunctional Heterogeneous Asym-
metric Catalysts for Sequential Reactions. J. Am. Chem. Soc. 2017,
139, 8259−8266.
(38) Feng, X.; Song, Y.; Li, Z.; Kaufmann, M.; Pi, Y.; Chen, J.; Xu,
Z.; Zhong, L.; Wang, C.; Lin, W. Metal-Organic Framework Stabilizes
A Low-Coordinate Iridium Complex for Catalytic Methane
Borylation. J. Am. Chem. Soc. 2019, 141, 11196−11203.
(39) Gui, B.; Yee, K.-K.; Wong, Y.-L.; Yiu, S.-M.; Zeller, M.; Wang,
C.; Xu, Z. Tackling poison and leach: catalysis by dangling thiol-
palladium functions within a porous metal-organic solid. Chem.
Commun. 2015, 51, 6917−6920.
(40) Yee, K.-K.; Wong, Y.-L.; Zha, M.; Adhikari, R. Y.; Tuominen,
M. T.; He, J.; Xu, Z. Room-temperature acetylene hydration by a
Hg(II)-laced metal-organic framework. Chem. Commun. 2015, 51,
10941−10944.
(41) Mon, M.; Rivero-Crespo, M. A.; Ferrando-Soria, J.; Vidal-
Moya, A.; Boronat, M.; Leyva-Perez, A.; Corma, A.; Hernandez-
Garrido, J. C.; Lopez-Haro, M.; Calvino, J. J.; Ragazzon, G.; Credi, A.;
Armentano, D.; Pardo, E. Synthesis of Densely Packaged, Ultrasmall
Pt02 Clusters within a Thioether-Functionalized MOF: Catalytic
Activity in Industrial Reactions at Low Temperature. Angew. Chem.,
Int. Ed. 2018, 57, 6186−6191.
(42) Fortea-Perez, F. R.; Mon, M.; Ferrando-Soria, J.; Boronat, M.;
Leyva-Perez, A.; Corma, A.; Herrera, J. M.; Osadchii, D.; Gascon, J.;
Armentano, D.; Pardo, E. The MOF-driven synthesis of supported
palladium clusters with catalytic activity for carbene-mediated
chemistry. Nat. Mater. 2017, 16, 760−766.
(43) Qin, J.-S.; Yuan, S.; Lollar, C.; Pang, J.; Alsalme, A.; Zhou, H.-
C. Stable metal-organic frameworks as a host platform for catalysis
and biomimetics. Chem. Commun. 2018, 54, 4231−4249.
(44) Carboni, M.; Abney, C. W.; Liu, S.; Lin, W. Highly porous and
stable metal-organic frameworks for uranium extraction. Chem. Sci.
2013, 4, 2396−2402.
(45) Yee, K.-K.; Reimer, N.; Liu, J.; Cheng, S.-Y.; Yiu, S.-M.; Weber,
J.; Stock, N.; Xu, Z. Effective Mercury Sorption by Thiol-Laced
Metal-Organic Frameworks: in Strong Acid and the Vapor Phase. J.
Am. Chem. Soc. 2013, 135, 7795−7798.
(46) Li, M.-Q.; Wong, Y.-L.; Lum, T.-S.; Sze-Yin Leung, K.; Lam, P.
K. S.; Xu, Z. Dense thiol arrays for metal-organic frameworks: boiling
water stability, Hg removal beyond 2 ppb and facile crosslinking. J.
Mater. Chem. A 2018, 6, 14566−14570.
(47) Zha, M.; Liu, J.; Wong, Y.-L.; Xu, Z. Extraction of palladium
from nuclear waste-like acidic solutions by a metal-organic framework
with sulfur and alkene functions. J. Mater. Chem. A 2015, 3, 3928−
3934.
(26) Qiu, Y.-C.; Yuan, S.; Li, X.-X.; Du, D.-Y.; Wang, C.; Qin, J.-S.;
Drake, H. F.; Lan, Y.-Q.; Jiang, L.; Zhou, H.-C. Face-Sharing
Archimedean Solids Stacking for the Construction of Mixed-Ligand
Metal-Organic Frameworks. J. Am. Chem. Soc. 2019, 141, 13841−
13848.
(27) Zhai, Q.-G.; Bu, X.; Zhao, X.; Li, D.-S.; Feng, P. Pore Space
Partition in Metal-Organic Frameworks. Acc. Chem. Res. 2017, 50,
407−417.
(28) Jacobsen, J.; Reinsch, H.; Stock, N. Systematic Investigations of
the Transition between Framework Topologies in Ce/Zr-MOFs.
Inorg. Chem. 2018, 57, 12820−12826.
(29) Waitschat, S.; Reinsch, H.; Arpacioglu, M.; Stock, N. Direct
water-based synthesis and characterization of new Zr/Hf-MOFs with
dodecanuclear clusters as IBUs. CrystEngComm 2018, 20, 5108−
5111.
(30) He, J.; Cheng, S.; Xu, Z. Sulfur Chemistry for Stable and
Electroactive Metal-Organic Frameworks: The Crosslinking Story.
Chem. - Eur. J. 2019, 25, 1−10.
E
https://dx.doi.org/10.1021/acs.inorgchem.0c00576
Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
pubs.acs.org/IC
Article
(48) Hou, Y.-L.; Yee, K.-K.; Wong, Y.-L.; Zha, M.; He, J.; Zeller, M.;
Hunter, A. D.; Yang, K.; Xu, Z. Metalation Triggers Single Crystalline
Order in a Porous Solid. J. Am. Chem. Soc. 2016, 138, 14852−14855.
(49) Mon, M.; Lloret, F.; Ferrando-Soria, J.; Martí-Gastaldo, C.;
Armentano, D.; Pardo, E. Selective and Efficient Removal of Mercury
from Aqueous Media with the Highly Flexible Arms of a BioMOF.
Angew. Chem., Int. Ed. 2016, 55, 11167−11172.
(50) Li, K.; Xu, Z.; Xu, H.; Ryan, J. M. Semiconductive
Coordination Networks from 2,3,6,7,10,11-Hexakis(alkylthio)-
triphenylenes and Bismuth(III) Halides: Synthesis, Structure-
Property Relations, and Solution Processing. Chem. Mater. 2005,
17, 4426−4437.
(51) Li, K.; Xu, Z.; Xu, H.; Carroll, P. J.; Fettinger, J. C. Three-
Dimensional Nets from Star-Shaped Hexakis(arylthio)triphenylene
Molecules and Silver(I) Salts. Inorg. Chem. 2006, 45, 1032−1037.
(52) Cui, J.; Xu, Z. An electroactive porous network from covalent
metal-dithiolene links. Chem. Commun. 2014, 50, 3986−3988.
(53) Zhou, X.-P.; Xu, Z.; Zeller, M.; Hunter, A. D.; Chui, S. S.-Y.;
Che, C.-M. Coordination Networks from a Bifunctional Molecule
Containing Carboxyl and Thioether Groups. Inorg. Chem. 2008, 47,
7459−7461.
(54) Wong, Y.-L.; Yee, K.-K.; Hou, Y.-L.; Li, J.; Wang, Z.; Zeller, M.;
Hunter, A. D.; Xu, Z. Single-Crystalline UiO-67-Type Porous
Network Stable to Boiling Water, Solvent Loss, and Oxidation.
Inorg. Chem. 2018, 57, 6198−6201.
(55) Chen, T.-H.; Popov, I.; Zenasni, O.; Daugulis, O.; Miljanic, O.
S. Superhydrophobic perfluorinated metal-organic frameworks. Chem.
Commun. 2013, 49, 6846−6848.
(56) Larionov, S. V.; Myachina, L. I.; Sheludyakova, L. A.; Korolkov,
I. V.; Rakhmanova, M. I.; Plyusnin, P. E.; Vinogradov, A. S.; Karpov,
V. M.; Platonov, V. E.; Fadeeva, V. P. Synthesis of Octafluor-
obiphenyl-4,4′-dicarboxylic acid and photoluminescent compounds
based thereon. Russ. J. Gen. Chem. 2015, 85, 1617−1622.
(57) Chavan, S.; Vitillo, J. G.; Gianolio, D.; Zavorotynska, O.;
Civalleri, B.; Jakobsen, S.; Nilsen, M. H.; Valenzano, L.; Lamberti, C.;
Lillerud, K. P.; Bordiga, S. H2storage in isostructural UiO-67 and
UiO-66 MOFs. Phys. Chem. Chem. Phys. 2012, 14, 1614−1626.
(58) DeCoste, J. B.; Peterson, G. W.; Jasuja, H.; Glover, T. G.;
Huang, Y.-g.; Walton, K. S. Stability and degradation mechanisms of
metal-organic frameworks containing the Zr6O4(OH)4 secondary
building unit. J. Mater. Chem. A 2013, 1, 5642−5650.
(59) Mondloch, J. E.; Katz, M. J.; Planas, N.; Semrouni, D.;
Gagliardi, L.; Hupp, J. T.; Farha, O. K. Are Zr6-based MOFs water
stable? Linker hydrolysis vs. capillary-force-driven channel collapse.
Chem. Commun. 2014, 50, 8944−8946.
(60) Lawrence, M. C.; Schneider, C.; Katz, M. J. Determining the
structural stability of UiO-67 with respect to time: a solid-state NMR
investigation. Chem. Commun. 2016, 52, 4971−4974.
F
https://dx.doi.org/10.1021/acs.inorgchem.0c00576
Inorg. Chem. XXXX, XXX, XXX−XXX