Beyond the Active Site: Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization

Article abstract of DOI:10.1021/jacs.8b06006

To modify its steric and electronic properties as a support for heterogeneous catalysts, electron-withdrawing and electron-donating ligands, hexafluoroacetylacetonate (Facac^-) and acetylacetonate (Acac^-), were introduced to the metal-organic framework (MOF), NU-1000, via a process akin to atomic layer deposition (ALD). In the absence of Facac^- or Acac^-, NU-1000-supported, AIM-installed Ni(II) sites yield a mixture of C4, C6, C8, and polymeric products in ethylene oligomerization. (AIM = ALD-like deposition in MOFs). In contrast, both Ni-Facac-AIM-NU-1000 and Ni-Acac-AIM-NU-1000 exhibit quantitative catalytic selectivity for C4 species. Experimental findings are supported by density functional theory calculations, which show increases in the activation barrier for the C-C coupling step, due mainly to rearrangement of the siting of Facac^- or Acac^- to partially ligate added nickel. The results illustrate the important role of structure-tuning support modifiers in controlling the activity of MOF-sited heterogeneous catalysts and in engendering catalytic selectivity. The results also illustrate the ease with which crystallographically well-defined modifications of the catalyst support can be introduced when the node-coordinating molecular modifier is delivered via the vapor phase.

Full text of DOI:10.1021/jacs.8b06006

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Communication
Beyond the Active Site: Tuning the Activity and Selectivity of a Metal
-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization
Jian Liu, Jingyun Ye, Zhanyong Li, Ken-ichi Otake, Yijun Liao, Aaron W. Peters, Hyunho Noh,
Donald G. Truhlar, Laura Gagliardi, Christopher J. Cramer, Omar K. Farha, and Joseph T. Hupp
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b06006 • Publication Date (Web): 24 Aug 2018
Downloaded from http://pubs.acs.org on August 24, 2018
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Beyond the Active Site: Tuning the Activity and Selectivity of a Metꢀ
al−Organic FrameworkꢀSupported Ni Catalyst for Ethylene Dimeriꢀ
zation
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†
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Jian Liu, Jingyun Ye, ⊥ Zhanyong Li, ⊥ Kenꢀichi Otake, Yijun Liao, Aaron W. Peters, Hyunho
⊥
†
‡
‡
‡
,†,§,
∥
Noh, Donald G. Truhlar, Laura Gagliardi, Christopher J. Cramer, Omar K. Farha*
and Joseph T.
,
†
Hupp*
†
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Department of Chemistry, Minnesota Supercomputing Institute, and Chemical Theory Center, University of Minnesota,
‡
Minneapolis, Minnesota 55455, United States.
§
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia.
∥
Department of Chemical and Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois
6
0208, United States.
Supporting Information Placeholder
1
0
and/or the interconnecting organic linkers, making them promisꢀ
ing materials for a broad range of potential applications, including
ABSTRACT: To modify its steric and electronic properties as a
support for heterogeneous catalysts, electronꢀwithdrawing and
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−
gas separation, gas storage and release, chemical sensing,
electronꢀdonating ligands, hexafluoroacetylacetonate (Facac ) and
14
−
and heterogeneous catalysis. NUꢀ1000, a MOF of scu topology
featuring Zr (ꢁ –O) (ꢁ –OH) (H O) (OH) clusters as nodes (abꢀ
acetylacetonate (Acac ), were introduced to the metal−organic
framework (MOF), NUꢀ1000, via a process akin to atomic layer
6
3
4
3
4
2
4
4
−
−
breviated as Zr6) and tetratopic 1,3,6,8ꢀ(pꢀbenzoate)pyrene
TBAPy ) units as linkers, has proven effective as a support for
wellꢀdefined oxyꢀmetal catalysts, including catalysts for ethylene
hydrogenation and oligomerization, propane oxidative dehydroꢀ
deposition (ALD). In the absence of Facac or Acac , NUꢀ1000ꢀ
supported, AIMꢀinstalled Ni(II) sites yield a mixture of C4, C6,
C8, and polymeric products in ethylene oligomerization. (AIM =
ALDꢀlike deposition in MOFs). In contrast, both NiꢀFacacꢀAIMꢀ
NUꢀ1000 and NiꢀAcacꢀAIMꢀNUꢀ1000 exhibit quantitative cataꢀ
lytic selectivity for C4 species. Experimental findings are supꢀ
ported by density functional theory calculations, which show inꢀ
creases in the activation barrier for the C–C coupling step, due
4−
15
(
16
17
18
genation, and alkene epoxidation.
Work in our labs has shown that vaporꢀphase “AIM” (ALDꢀlike
chemistry in MOFs) is effective for assembling uniform arrays of
catalytically active, metalꢀoxygen and metalꢀsulfur clusters directꢀ
For example, the material, NiꢀAIMꢀNUꢀ
1000, exhibits high activity for ethylene oligomerization upon
addition of the coꢀcatalyst, (CH CH ) AlCl. However, this cataꢀ
−
−
16,18
mainly to rearrangement of the siting of Facac or Acac to parꢀ
tially ligate added nickel. The results illustrate the important role
of structureꢀtuning support modifiers in controlling the activity of
MOFꢀsited heterogeneous catalysts and in engendering catalytic
selectivity. The results also illustrate the ease with which crystalꢀ
lographically wellꢀdefined modifications of the catalyst support
can be introduced when the nodeꢀcoordinating molecular modifier
is delivered via the vapor phase.
ly on MOF nodes.
3
2 2
lyst generates a wide distribution of products, including C4, C6,
and C8, as well as undesirable polymeric material.
16a
Catalysts that selectively facilitate the production of C4 (1ꢀ
butene) from ethylene are of great interest since 1ꢀbutene is a
widely used coꢀmonomer in the commercial gasꢀphase synthesis
of linear lowꢀdensity polyethylene. We reasoned that appropriate
tuning of the steric and electronic environment near the Ni(II)
active site of NiꢀAIMꢀNUꢀ1000 might modulate its activity and/or
catalytic chemical selectivity. As a starting point, and as a proofꢀ
ofꢀconcept, we first introduced highly electronꢀwithdrawing or
Heterogeneous catalysis is central to chemical and polymer
1
manufacturing, a variety of environmental remediation processꢀ
2
3
es, and many other chemoꢀcentric endeavors. Appropriately
chosen supports can be used to modulate the electronic properties
of deposited active species, potentially yielding desirable changes
weakly electronꢀdonating ligands for Zr , hexafluoroacetyꢀ
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−
−
lacetonate (Facac ) or acetylacetonate (Acac ), followed by AIM
installation of Ni(II); the resulting materials are termed NiꢀFacacꢀ
AIMꢀNUꢀ1000 and NiꢀAcacꢀAIMꢀNUꢀ1000, respectively (Figure
4
,5
6ꢀ8
in catalyst activity or chemical selectivity. Inorganicꢀoxides
constitute a widely studied and broadly effective family of supꢀ
ports. Nevertheless, fineꢀtuning support properties using solely
inorganic components can be challenging. We reasoned that metꢀ
alꢀorganic frameworks (MOFs), could function as both broadly
and finely tunable heterogeneousꢀcatalyst supports; here we preꢀ
sent such results.
1
). Notably, supportꢀligand installation was accomplished via
volatilization, vaporꢀphase delivery of, and MOFꢀpermeation by
the conjugate acids, HFacac and HAcac, concomitant with release
of aqua and hydroxo ligands. The organic elaboration brought
about distinct decreases in catalytic activity for ethylene oliꢀ
gomerization. Also seen, however, was a remarkable increase in
product selectivity, i.e. exclusive formation of C4 (butene), with
an overwhelming preference for the isomer, 1ꢀbutene. Density
MOFs constitute a large and growing class of porous, crystalꢀ
9
line materials. Broad tuning of MOF physical and chemical
properties is achievable via modulation of metalꢀcontaining nodes
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functional theory (DFT) modeling provides key insights into the
mechanistic basis for high catalytic chemical selectivity.
coordination of Facac , the binding energy shifts from 182.9 to
183.3 eV; after Ni installation, it shifts slightly back to higher
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energy. These observations imply electronic communication beꢀ
−
tween Facac ligands, Zr nodes, and grafted Ni(II), behavior that
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was computationally probed by CM5 charge analysis. (Table
S2) The electronic effect of the more weakly electronꢀdonating
Acac ligands is not obvious in the XPS data. Detailed characteriꢀ
−
zation (SEM/EDS, powder XRD and N isotherms) of all samples
2
indicated little difference in MOF crystallinity, particle morpholꢀ
ogy, or porosity (Figures S6–S8), thus underscoring the structural
stability of the MOF with respect to node elaboration.
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Figure 1. Schematic depiction of installation of the monoꢀanionic
−
Facac ligand and Ni ions to the Zr nodes of NUꢀ1000. Color: C,
6
grey; H, white; O, red; F, green; Ni, purple; Zr, cyan. (For clarity,
linkers are truncated and shown as formate groups.) The indicated
ꢀ
partial ligation of added Ni by Facac is derived from computaꢀ
tions.
Due to the strong electronꢀwithdrawing character of –CF3
groups the single oxygenꢀbound proton is sufficiently acidic that
Figure 2. (a) Xꢀray absorption nearꢀedge spectra (XANES) and
(b) extended Xꢀray absorption fine structure spectra (EXAFS) for
NiꢀFacacꢀAIMꢀNUꢀ1000, NiꢀAcacꢀAIMꢀNUꢀ1000 and NiꢀAIMꢀ
−
ligation of Facac to MOF nodes via a process similar to solventꢀ
1
9
assisted ligand incorporation (SALI) is expected. Because of the
high vapor pressure of HFacac, Facac anions can be installed
within NUꢀ1000 via the molecular equivalent of ALD. Acac aniꢀ
NUꢀ1000, and reference Ni(OH) ; (c) conversion vs. W/F for
2
ethylene dimerization catalyzed by activated NiꢀFacacꢀAIMꢀNUꢀ
1000 and NiꢀAcacꢀAIMꢀNUꢀ1000; (d) product distribution for
ethylene oligomerization as catalyzed by activated NiꢀFacacꢀ
AIMꢀNUꢀ1000 and NiꢀAcacꢀAIMꢀNUꢀ1000 compared to Niꢀ
AIMꢀNUꢀ1000. Note: data for NiꢀAIMꢀNUꢀ1000 are from referꢀ
ence 16a. (W=mol catalyst; F=flowrate reactant (mol/s))
−
ons can be introduced in the same way. Acac incorporation can
1
be quantified via H spectroscopy, showing ~ 2.8 ± 0.1 ligands
per Zr node before and after Ni AIM process. A combination of
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H and F NMR spectroscopy was used to quantify Facac incorꢀ
poration, giving an average loading of ~ 2.5 ± 0.2 ligands per Zr6
node (Figure S1).
Xꢀray absorption spectroscopy was employed to probe the vaꢀ
lence and size of the Niꢀoxo clusters in NiꢀFacacꢀAIMꢀNUꢀ1000
and NiꢀAcacꢀAIMꢀNUꢀ1000. Observable in the Xꢀray absorption
nearꢀedge spectral (XANES) region (Figure 2 a), is weak preꢀedge
peak corresponding to the 1s→3d transition at 8333.3 eV. This
peak is indicative of divalent nickel, as observed in the Ni(II)
Diffuse reflectance infrared Fourier transform spectra suggest
that the strength of binding of –OH to nodes is altered by binding
−
−
Acac or Facac to the nodes, as the –OH stretching frequency
−1
shifts from 3674 to 3651 or 3642 cm , respectively (Figure S2).
−
One can imagine two possible modes of ligation for (F)acac :
bridging between pairs of Zr(IV) ions or singleꢀligand chelation of
one Zr(IV). Singleꢀcrystal Xꢀray diffraction of the “molecular
AIM” functionalized material revealed that each Facac anion
chelates a single Zr ion (Figure S3 c & d) where the ligands point
toward the hexagonal channels and toward pores perpendicular to
the c-axis (Figures S3 a & b and Table S1).
standard (Ni(OH) ) and in NiꢀAIMꢀNUꢀ1000. In the Fourier transꢀ
2
formed extended Xꢀray absorption fine structure (EXAFS) specꢀ
trum, the dominant peak appears at a phaseꢀuncorrected distance
of ~1.62 Å; it can be fitted to a Ni−O scattering path featuring a
bond length of 2.03 ± 0.01 and 2.05 ± 0.01 Å for NiꢀFacacꢀAIMꢀ
NUꢀ1000 and NiꢀAcacꢀAIMꢀNUꢀ1000, respectively. (Figures 2b,
S9, S10, and S11 and Table S3.) The peak at 2.73 Å, which has
Retention of –OH stretches in the IR spectrum implies that Faꢀ
cacꢀAIMꢀNUꢀ1000 and AcacꢀAIMꢀNUꢀ1000 can be further funcꢀ
tionalized with Ni(II). Using a procedure similar to that for Niꢀ
AIMꢀNUꢀ1000, the new materials, NiꢀFacacꢀAIMꢀNUꢀ1000 and
NiꢀAcacꢀAIMꢀNUꢀ1000, were produced. The incorporation of Ni
16a
been ascribed previously to Ni−Ni scattering,
weaker here than that in the EXAFS spectrum of NiꢀAIMꢀNUꢀ
000, implying a slightly smaller Niꢀoxo cluster in the Faꢀ
is marginally
1
cac/Acacꢀmodified materials. This inference is in line with the
results of inductively coupled plasma atomic emission spectrosꢀ
copy (ICPꢀAES) results, which indicate Ni loadings of 3.4 ± 0.3,
−
ions and retention of Facac ligands after the NiꢀAIM were conꢀ
firmed via Xꢀray photoelectron spectroscopy (XPS) (Figures S4 &
S5). Important differences between the XPS spectra of NUꢀ1000,
FacacꢀAIMꢀNUꢀ1000, and NiꢀFacacꢀAIMꢀNUꢀ1000 are the inꢀ
ferred values of the Zr 3d5/2 binding energy (Figure S4 a). Upon
3
.5 ± 0.4 and 4.0 ± 0.3 Ni/Zr for NiꢀFacacꢀAIMꢀNUꢀ1000, Niꢀ
6
AcacꢀAIMꢀNUꢀ1000 and NiꢀAIMꢀNUꢀ1000 to be, respectively.
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To probe the effects of Acac and Facac ligands on the catalytꢀ
ic behavior of NiꢀAIMꢀNUꢀ1000, we examined the gasꢀphase
oligomerization of ethylene. The three materials exhibit qualitaꢀ
tively similar catalytic behavior during the first 10 h timeꢀonꢀ
stream (TOS), viz. (Figure S12a) modest decreases in catalytic
activity presumably due to initial formation of polymeric prodꢀ
ucts. C4 and C6 were also observed during the first 10 h TOS
(F)acac to partially ligate added nickel (Figures 1 and 3; data in
Tables S5 and S6).
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(
Figure S12b). The turnover frequency (TOF) (on a perꢀnickelꢀ
atom basis) gradually decreases – ultimately stabilizing, after ~10
h, at (3.5 ± 0.78) × 10 s for NiꢀFacacꢀAIMꢀNUꢀ1000 and (4.4 ±
0
lower than that for the modifierꢀfree catalyst (0.07 s ). Accomꢀ
panying TOF stabilization is a refinement of the product distribuꢀ
tion such that NiꢀFacacꢀAIMꢀNUꢀ1000 and NiꢀAcacꢀAIMꢀNUꢀ
ꢀ
3 −1
ꢀ
3 −1
.85) × 10 s for NiꢀAcacꢀAIMꢀNUꢀ1000 (Figure 2c), ~20 times
ꢀ1 16a
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000 both catalyze only C4 formation. In striking contrast, the
unmodified catalyst even after several hours on stream, yields a
mixture of C4, C6, and C8 products (Figure 2d). Characterization
of the postꢀcatalysis versions of NiꢀFacacꢀAIMꢀNUꢀ1000 and Niꢀ
AcacꢀAIMꢀNUꢀ1000 (Figures S13−S16) reveals retention of the
original microparticle morphology and crystallinity, and retention
−
−
of postꢀsynthetically installed Facac /Acac and Ni(II).
Figure 3. Gibbs free energy profiles (298.15 K, 1 atm) for the
stationary points along reaction coordinates for ethylene oliꢀ
gomerization catalyzed by NiꢀAcacꢀAIMꢀNUꢀ1000 and NiꢀFacacꢀ
AIMꢀNUꢀ1000 compared to NiꢀAIMꢀNUꢀ1000. Solid and dash
lines represent C2 to C4 and C4 to C6 reaction paths, respectively.
Depictions of species in the catalytic cycle include only selected
atoms for clarity.
To understand the greatly enhanced selectivity for C4 engenꢀ
dered by elaborating the hexaꢀzirconium node (itself catalytically
inactive), a Gibbs free energy profile was computationally modꢀ
22
eled based on the proposed Zr node structure model (Figure S17).
6
While this model employs a single Ni atom in lieu of a larger Niꢀ
oxo cluster, it should permit qualitative exploration of the influꢀ
ence of the installed ligands. (Thus, previous computations have
shown single Ni atoms to be a good model for Ni clusters specifꢀ
ically for understanding the catalytic activity of nonꢀelaborated
NiꢀAIMꢀNUꢀ1000 for ethylene dimerization. ) As illustrated in
Figure 3, the catalytic cycle starts with the activated species 1,
where the ethyl group binds to Ni(II) via a strong βꢀagostic interꢀ
action with one H of the CH group.
ylene binds to 1 at Ni(II) leading to the formation of 2, which is
exergonic by 8.3 kcal/mol for NiꢀFacacꢀAIMꢀNUꢀ1000. With a
2
Ni–C bond to produce 3 via transitionꢀstate (TS) structure TS2–3.
With a subsequent free energy of activation of 9.6 kcal/mol (TS3–
4
comitant formation of a nickel hydride species. After 1ꢀbutene
desorption, ethylene can react with the nickel hydride species to
reform 1. Alternatively, 3 can further react with another ethylene
molecule to produce a more stable structure 6 (5.4 kcal/mol lower
than 3 in free energy). However, the migratory insertion of ethꢀ
ylene into the Ni–C bond in 6 to produce Ni–hexyl species 7 reꢀ
quires going through transition structure TS6–7 with a 24.5
kcal/mol free energy of activation, which is 9.5 kcal/mol higher
than that to produce 1ꢀbutene. Therefore, the production of 1ꢀ
butene is more favorable than the chain growth process to make
oligomeric products, in line with the experimental observation
In summary, molecular modifiers of MOF supports for heteroꢀ
geneous catalysts can be introduced in atomically precise fashion
via an ALDꢀlike, vaporꢀphase delivery mechanism. For NUꢀ1000,
4
21
−
−
the modifiers Facac and Acac , displace node aqua and hydroxo
ligands and bind to Zr(IV) in chelating fashion, as evidenced by
singleꢀcrystal Xꢀray diffraction. Compared with the modifierꢀfree
catalyst (NiꢀAIMꢀNUꢀ1000), the new materials, NiꢀFacacꢀAIMꢀ
NUꢀ1000 and NiꢀAcacꢀAIMꢀNUꢀ1000, exhibit lower catalytic
activity but remarkable changes in product selectivity for oliꢀ
gomerization of ethylene – most notably, exclusive formation of
C4 (butene) species with a strong preference of the 1ꢀbutene isoꢀ
mer. DFT free energy profiles point to energetically more favoraꢀ
ble butene release and diminished energetic access to a CꢀC bond
forming, chain propagation step, when the support modifiers are
present. The effects arise mainly from rearrangement of the siting
1
6a, 16b, 22
An incoming ethꢀ
3
6.6 kcal/mol free energy of activation, ethylene inserts into the
), 1ꢀbutene is produced via βꢀhydrogen elimination with the conꢀ
−
−
of Facac or Acac and, therefore, partial ligation of added nickel
Figure 1). The strategy of automated, vaporꢀphaseꢀmediated,
(
modular assembly of uniform arrays of increasingly complex
catalytic systems appears to provide a versatile way to fineꢀtune
properties of the activeꢀsite, and to predictably define and control
the chemical environment beyond the catalyst’s active site.
ASSOCIATED CONTENT
(
vide supra); NiꢀAcacꢀAIMꢀNUꢀ1000 shows similar selectivity to
Supporting Information
NiꢀFacacꢀAIMꢀNUꢀ1000 for 1ꢀbutene production because the free
energy of activation for Niꢀhexyl production (23.2 kcal/mol) is
11.2 kcal/mol higher than that for 1ꢀbutene production (Table S4).
Also noteworthy is the computation that the activation barrier for
the first C‒C coupling step of unmodified NiꢀAIMꢀNUꢀ1000 (2→
The Supporting Information is available free of charge on the
ACS
Publications
website.
Materials synthesis, characterization data and computational
details
(PDF).
Xꢀray crystallography for FacacꢀAIMꢀNUꢀ1000 (CIF).
3
) (13.7 kcal/mol) is 12.9 kcal/mol lower than that for NiꢀFacacꢀ
AIMꢀNUꢀ1000, consistent with the higher activity for ethylene
oligomerization observed for the former. The lower activity of Niꢀ
Facac/AcacꢀAIMꢀNUꢀ1000 for ethylene dimerization derives
partly from stronger binding of substrate to Ni and partly from
greater costs for structural deformation along C‒C coupling reacꢀ
tion pathways, likely due to rearrangement of the siting of
AUTHOR INFORMATION
Corresponding Authors
*
*
O. K. F. (oꢀfarha@northwestern.edu)
J. T. H. (jꢀhupp@northwestern.edu)
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(10) (a) Zhou, T.; Du, Y.; Borgna, A.; Hong, J.; Wang, Y.; Han, J.; Zhang,
Author Contributions
W.; Xu, R. Energy Environ. Sci. 2013, 6, 3229. (b) Martell, J. D.; Porterꢀ
Zasada, L. B.; Forse, A. C.; Siegelman, R. L.; Gonzalez, M. I.;
Oktawiec, J.; Runcevski, T.; Xu, J.; SrebroꢀHooper, M.; Milner, P. J.;
Colwell, K. A.; Autschbach, J.; Reimer, J. A.; Long, J. R. J. Am. Chem.
Soc. 2017, 139, 16000. (c) Flaig, R. W.; Osborn Popp, T. M.; Fracaroli,
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⊥These
Notes
authors
contributed
equally.
The authors declare no competing financial interests.
ACKNOWLEDGMENTS
This work was supported as part of the Inorganometallic Catalyst
Design Center, an EFRC funded by the DOE, Office of Science,
Basic Energy Sciences (DEꢀSC0012702). H. N. gratefully
acknowledges support from the Ryan Fellowship and the
(12) (a) Liao, Y.; Zhang, L.; Weston, M. H.; Morris, W.; Hupp, J. T.;
Farha, O. K. Chem. Commun. 2017, 53, 9376. (b) Murray, L. J.; Dinca,
M.; Long, J. R. Chem. Soc. Rev. 2009, 38, 1294. (c) Peng, Y.;
Krungleviciute, V.; Eryazici, I.; Hupp, J. T.; Farha, O. K.; Yildirim, T. J.
Am. Chem. Soc. 2013, 135, 11887.
Northwestern
University
International
Institute
of
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Nanotechnology. This work made use of the J.B. Cohen Xꢀray
Diffraction Facility supported by the MRSEC program of the
National Science Foundation (DMRꢀ1121262) at the Materials
Research Center of Northwestern University. This work made use
of the EPIC and KeckꢀII facilities of the NUANCE Center at
Northwestern University, which has received support from the
Soft and Hybrid Nanotechnology Experimental (SHyNE)
Resource (NSF NNCIꢀ1542205); the MRSEC program (NSF
DMRꢀ1121262) at the Materials Research Center; the
International Institute for Nanotechnology (IIN); the Keck
Foundation; and the State of Illinois, through the IIN. Use of the
Advanced Photon Source is supported by the U.S. Department of
Energy, Office of Science, and Office of Basic Energy Sciences,
under Contract DEꢀAC02ꢀ06CH11357. Materials Research
Collaborative Access Team (MRCAT, Sector10ꢀBM) operations
are supported by the Department of Energy and the MRCAT
member institutions.
(13) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, R.
P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105.
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Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450. (b) Zhang, X.; Vermeulen, N.
A.; Huang, Z.; Cui, Y.; Liu, J.; Krzyaniak, M. D.; Li, Z.; Noh, H.;
Wasielewski, M. R.; Delferro, M.; Farha, O. K. ACS Appl. Mater. Inter-
faces 2018, 10, 635. (c) Bernales, V.; Ortuño, M. A.; Truhlar, D. G.;
Cramer, C. J.; Gagliardi, L. ACS Central Sci. 2018, 4, 5.
(15) Planas, N.; Mondloch, J. E.; Tussupbayev, S.; Borycz, J.; Gagliardi,
L.; Hupp, J. T.; Farha, O. K.; Cramer, C. J. J. Phys. Chem. Lett. 2014, 5,
3716.
(16) (a) Li, Z.; Schweitzer, N. M.; League, A. B.; Bernales, V.; Peters, A.
W.; Getsoian, A. B.; Wang, T. C.; Miller, J. T.; Vjunov, A.; Fulton, J. L.;
Lercher, J. A.; Cramer, C. J.; Gagliardi, L.; Hupp, J. T.; Farha, O. K. J.
Am. Chem. Soc. 2016, 138, 1977. (b) Bernales, V.; League, A. B.; Li, Z.;
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