Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities

Article abstract of DOI:10.1002/anie.201809493

Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an Ir^III photoredox catalyst and a Ni^II cross-coupling catalyst into a stable Zr₁₂ MOF, Zr₁₂-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the Ir^III and Ni^II catalytic components to each other (ca. 0.6 nm) in Zr₁₂-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.

Full text of DOI:10.1002/anie.201809493

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Accepted Article
Title: Merging Photoredox and Organometallic Catalysts in a Metal-
Organic Framework Significantly Boosts Photocatalytic Activities
Authors: Yuan-Yuan Zhu, Guangxu Lan, Yingjie Fan, Samuel
Veroneau, Yang Song, Daniel Micheroni, and Wenbin Lin
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201809493
Angew. Chem. 10.1002/ange.201809493
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10.1002/anie.201809493
Angewandte Chemie International Edition
COMMUNICATION
Merging Photoredox and Organometallic Catalysts in a Metal-
Organic Framework Significantly Boosts Photocatalytic Activities
Yuan-Yuan Zhu+,[a,b] Guangxu Lan+,[a] Yingjie Fan,[a,c] Samuel S. Veroneau,[a] Yang Song,[a] Daniel
Micheroni,[a] and Wenbin Lin*[a]
Abstract: Metal-organic frameworks (MOFs) have been extensively
used for single-site catalysis and light harvesting, but their application
in multicomponent photocatalysis is unexplored. We report here the
successful incorporation of IrIII photoredox and NiII cross-coupling
catalysts into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C−S
bond formation between various aryl iodides and thiols. The proximity
of IrIII photoredox and NiII cross-coupling catalytic components (~0.6
nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers
from Ir to Ni centers to reach a turnover number of 38500, an order of
magnitude higher than that of its homogeneous counterpart. This work
highlights the opportunity in merging photoredox and organometallic
catalysts in MOFs to effect challenging organic transformations.
photoredox and organometallic dual catalysts in a MOF and its
application in visible-light driven cross-coupling between aryl
iodides and aryl thiols (Figure 1).
Metal-organic frameworks (MOFs) are crystalline porous
materials built from metal ions or clusters bridged by organic
linkers.[1] MOFs have been employed to study light harvesting[2]
and single-site catalysis.[3] Progress has also been made in
incorporating photosensitizing components and catalytically
active functionalities into MOFs to afford photocatalytic systems
for H2 and O2 evolution and CO2 reduction, key half reactions for
artificial photosynthesis.[4] However, few MOFs have been
developed to catalyze organic photoreactions,[5] and all of them
were based on single components that served the role of
photosensitization.
Considering the success of MOFs in artificial photosynthesis,[2-
we posited that MOFs might provide a highly tunable platform
3]
Figure 1. Merging photoredox Ir and cross-coupling Ni catalysts in a Zr12 MOF
enhances photocatalytic activities.
to combine photoredox and transition metal catalysts to drive
multicomponent
organic
photoreactions.[6]
Such
MOF
photocatalysts should provide several benefits: (1) high local
concentrations (0.1-1 M) of photoredox and transition metal
catalysts in MOFs and their periodic arrangements facilitate the
transfer of electrons and radicals to accelerate the catalytic cycle;
(2) site isolation of transition metal catalysts prevent bimolecular
deactivation to stabilize the photocatalytic systems; (3) pore
confinement stabilizes photoredox catalysts in MOFs via a
rebound mechanism; (4) MOF photocatalysts can be readily
recycled and reused. Herein we report the first attempt at merging
The dual catalytic MOF Zr12-Ir-Ni containing [IrIII(dF(CF3)-
ppy)2(DBB)]Cl photosensitizer [H2L; where dF(CF3)ppy is 2-(2,4-
difluorophenyl)-5-(trifluoromethyl)pyridine and DBB is 4,4'-di(4-
benzoato)-2,2'-bipyridine] and (DBB)NiCl2 precatalyst was
synthesized via a combination of pre-functionalization and
postsynthetic
modification.
First,
treatment
of
[IrIII(dF(CF3)ppy)2]2Cl2 with Me2DBB afforded ([IrIII(dF(CF3)-
ppy)2(Me2DBB)]Cl) (Me2L) which was hydrolyzed under mild
basic condition to yield the ligand H2L (see SI for synthetic details).
A Zr12-type MOF, Zr12-Ir, was subsequently synthesized via a
solvothermal reaction between ZrCl4 and mixed ligands of H2DBB
and H2L in dimethylformamide (DMF) at 80 °C using acetic acid
as the modulator. 1H NMR analysis of the digested Zr12-Ir gave a
DBB to L ratio of approximately 1:1 (Figure S1, SI), affording a
[a]
[b]
Prof. Yuan-Yuan Zhu,[+] Guangxu Lan,[+] Yingjie Fan, Samuel S.
Veroneau, Yang Song, Daniel Micheroni, and Prof. Wenbin Lin*
Department of Chemistry, the University of Chicago
929 E 57th Street, Chicago, Illinois 60637, (USA)
E-mail: wenbinlin@uchicago.edu
framework
formula
of
Zr12(μ3-O)8(μ3-OH)8(μ2-
Prof. Yuan-Yuan Zhu[+]
OH)6(DBB)4.5[IrIII(dF(CF3)ppy)2(DBB)]4.5. Transmission electron
microscopy (TEM) imaging showed that Zr12-Ir adopted
hexagonal plate morphology (Figure 2a). High-resolution TEM
(HRTEM) imaging and fast Fourier transform (FFT) of Zr12-Ir
nanoplates revealed a 6-fold symmetry (Figure 2b), consistent
with the projection of the Zr12-Ir structure in the (001) direction.
Powder X-ray diffraction (PXRD) studies indicated that Zr12-Ir is
isostructural with recently reported Hf12-DBP (Figure 2d).[7]
School of Chemistry and Chemical Engineering, Hefei University of
Technology
Hefei 230009 (China)
[c]
[+]
Yingjie Fan
College of Chemistry and Molecular Engineering, Peking University,
Beijing 100871 (China)
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/anie.201809493
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Postsynthetic metalation of Zr12-Ir with NiCl2∙6H2O afforded
Zr12-Ir-Ni whose PXRD pattern and TEM image were unchanged
from Zr12-Ir (Figure 2c, d). The Ni content in Zr12-Ir-Ni MOF was
determined to be 4.43 Ni per Zr12 SBU by inductively coupled
plasma-mass spectrometry (ICP-MS), indicating complete
metalation of DBB ligands. Thermogravimetric analysis also
supported the complete coordination of DBB ligands with NiCl2 in
Zr12-Ir-Ni (Figure S2, SI). The porous structures of Zr12-Ir and Zr12-
Ir-Ni were evaluated by nitrogen sorption isotherms at 77 K
(Figure 2f) with Brunauer-Emmett-Teller (BET) surface areas of
580.6 and 472.3 m2/g, respectively. The extended X-ray
absorption fine structure (EXAFS) spectrum of Zr12-Ir-Ni was well
fitted with the model complex (bpy)NiCl2, indicating a tetrahedral
coordination environment for NiII centers in Zr12-Ir-Ni (Figure 2e
and Figure S7, SI).
cross-couplings of aryl iodides and thiophenols.[9] We decided to
test the applicability of Zr12-Ir-Ni as a photoredox and Ni dual
catalyst in this type of cross-coupling reactions and to gain
fundamental insights into designing multifunctional MOFs for
photocatalytic reactions.
Upon irradiation with blue LED (5 mW/cm2, 410 nm), stirring a
1.0 M acetonitrile solution of 4-iodobenzotrifluoride (1a) and 4-
methoxylthiophenol (2a) in the presence of 0.02 mol% Zr12-Ir-Ni
and 2,6-lutidine (2 equiv.) at r.t. for 48
h afforded (4-
methoxyphenyl)(4-(trifluoromethyl)phenyl)sulfane (3a) in 91%
yield (Table 1, entry 1), which corresponds to a turnover number
(TON) of 4550. By lowering the Zr12-Ir-Ni loading to 0.002 mol%,
a more impressive TON of 22500 was obtained (Table 1, entry 2).
Control experiments verified that the nickel complex,
photosensitizer, and light are all indispensable for this reaction
(Table S2, SI). In addition, 2,6-lutidine and pyridine gave the best
results among a series of organic bases examined (Table S2, SI).
Acetonitrile was the best solvent among several polar solvents
tested (Table S2, SI) while nonpolar solvents afforded only trace
amounts of 3a.
Table 1. Cross-coupling of Aryl Iodide and Thiophenol Using Zr12-Ni-Ir as a
Photoredox/Ni dual Catalyst.
Entry
Reaction conditions
Zr12-Ir-Ni (0.02 mol%)[a]
Zr12-Ir-Ni (0.002 mol%)[a]
C1 (0.002 mol%)[b]
Conv (%)[e]
TON
4550
22500
2850
1100
< 50
1
2
3
4
5
91
45
5.7
2.2
< 0.1
C2 (0.002 mol%)[c]
C3 (0.002 mol%)[d]
[a] Standard MOF conditions: aryl iodide (0.5 mmol), thiophenol (0.75 mmol),
2,6-lutidine (1.0 mmol), Zr12-Ir-Ni (0.25 mg, 0.02 mol% loading or 0.025 mg,
0.002 mol% loading) in MeCN (0.5 mL, 1.0 M aryl iodide concentration). [b]
Homogeneous control 1 (C1): (dtbppy)NiCl2∙and Me2L instead of Zr12-Ir-Ni.
[c] Homogeneous control 2 (C2): (dtbppy)NiCl2 and Zr12-Ir-QPDC instead of
Zr12-Ir-Ni. [d] Heterogeneous control (C3): Zr6-Ni-QPDC-NO2 and Zr12-Ir-
QPDC instead of Zr12-Ir-Ni. [e] Conversions were determined by GC-MS.
We performed two homogeneous control reactions under
identical conditions (1.0 M aryl iodide and 0.002 mol% catalyst
loading) to probe the advantages of this MOF-based dual catalyst.
First, 3a was obtained in only 5.7% conversion when
(dtbbpy)NiCl2 (dtbbpy is 4,4'-di-tert-butyl-2,2'-bipyridine) and
Me2L (C1) were used in place of Zr12-Ir-Ni (Table 1, Entry 3). The
corresponding TON of 2850 is almost 8 times lower than that of
Zr12-Ir-Ni. Second, when (dtbbpy)NiCl2 and Zr12-Ir-QPDC were
used as the catalysts (C2), and the conversion was only 2.2%
(TON = 1100), ~20 times lower than that of Zr12-Ir-Ni. Additionally,
a heterogeneous control reaction catalyzed by a physical mixture
of Zr6-Ni-QPDC-NO2 and Zr12-Ir-QPDC was conducted and only
a trace amount of the product was detected with a TON of < 50.
Figure 2. TEM image (a) and HRTEM image and FFT pattern (inset) (b) of Zr12
-
Ir. (c) TEM image of Zr12-Ir-Ni. (d) PXRD patterns of Hf12-DBP (black), Zr12-Ir
(red), Zr12-Ir-Ni (blue), and Zr12-Ir-Ni after photocatalysis (green). (e) EXAFS
spectra and the fits in R-space at the Ni K-edge of Zr12-Ir-Ni showing magnitude
(solid lines) and real component (hollow squares) of the Fourier transform. (f)
Nitrogen sorption isotherms of Zr12-Ir and Zr12-Ir-Ni at 77 K.
The prevalence of C−S bonds in organic chemicals and
pharmaceuticals has spurred continuous interest in developing
efficient methods for C−S bond formation.[8] In 2016, Oderinde et
al and Jouffroy et al reported photoredox and Ni dual catalysts for
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These results provide preliminary evidence for the synergy
between IrIII and NiII centers in Zr12-Ir-Ni, likely via enhanced
electron and radical transfers as well as increased stability of Ir
and Ni catalysts in the MOF. Time-dependent conversions
confirmed that Zr12-Ir-Ni was ~8 times active than C1 at 0.02
mol % catalyst loading throughout the 16 h reaction (Figure 3a).
These results clearly demonstrated the advantage of Zr12-Ir-Ni
over its homogeneous counterparts in photocatalytic cross-
coupling reactions.
iodides containing methyl group, thiols bearing benzyl and
cyclohexyl groups, and a cysteine derivative all underwent cross-
coupling reactions at a 0.02 mol% Zr12-Ir-Ni loading to afford the
desired products (3p to 3ac) in good to excellent yields (60-99%)
and TONs (3000-4950). Impressively, for the most reactive
substrates 1b (R1 = CN) and 2c (R2 = H), the cross-coupled
product 3f was obtained in 77 % yield at 0.002 mol% loading of
Zr12-Ir-Ni, corresponding to an impressive TON of 38500. Under
the same condition, C1 afforded 3f in 7.4% yield with a TON of
3700. Zr12-Ni-Ir could be recovered and reused for at least 5 times
for the synthesis of 3f without loss of catalytic activity (Figure 3b).
The MOF recovered from the photoreaction remained crystalline
as shown by PXRD (Figure 2d) with < 0.5% leaching of Ir and
non-detectable leaching of Ni. Simple mixing Zr12-Ir and Ni(NO3)2
in solution generated the dual catalyst in situ which afforded the
desired cross-coupling product in an excellent yield.
Table 2. Substrate Scope of Zr12-Ni-Ir catalyzed Cross-coupling between
Aryl Iodides Thiols.
Figure 3. (a) Plots of conversion vs. time at 0.02 mol% catalyst loading of Zr12
-
[a] 2,6-lutidine, rt. [b] pyridine, 55 °C. [c] Isolated yield. [d] TON.
Ir-Ni and C1. The conversions were determined by GC-MS. (b) Plots of yields
(%) of 3f catalyzed by recovered Zr12-Ir-Ni (0.02 mol% catalyst loading) in six
consecutive runs. (c) Emission spectra of Zr12-Ir (2  10−5 M, MeCN) after the
addition of different amounts of 2a with 365 nm excitation. (d) CVs of Me2L in
0.1 M TBAH/MeCN and [Ni(Me2DBB)]Cl2 in 0.1 M TBAH/DMF on a glassy
carbon disk working electrode with a Pt counter electrode and Ag wire quasi-
reference. Potential sweep rate was 100 mV/s. (e) Proposed mechanism for the
C−S cross coupling reaction catalyzed by Zr12-Ir-Ni.
We then investigated the substrate scope of this MOF-
catalyzed cross-coupling reaction (Table 2). In the presence of
0.02 mol% Zr12-Ir-Ni, reactions of diverse aryl iodides containing
various functional groups, including trifluoromethyl, cyano, formyl,
acetyl, and carbomethoxy groups, and three different aryl thiols
bearing hydrogen, methyl, and methoxy groups afforded
corresponding coupling products in excellent yields (86-96%) and
high TONs (4300-4800). Upon gentle heating at 55 °C, aryl
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10.1002/anie.201809493
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COMMUNICATION
Finally, we probed the reaction mechanism of Zr12-Ir-Ni
catalyzed C-S bond formation by photophysical and
electrochemical measurements. We first determined if electron
transfer between excited IrIII complex ([IrIII]*) in Zr12-Ir and
thiophenol or aryl iodide could occur by performing luminescence
quenching and cyclic voltammetric (CV) experiments. [IrIII]*
Luminescence of Zr12-Ir was quenched by both 4-
iodobenzotrifluoride (1a) and 4-methoxylthiophenol (2a), which
was fit to the Stern−Völmer equation to afford a KSV(1a) of 0.101
± 0.003 and a KSV(2a) of 0.365 ± 0.012 (Figure S56, SI and Figure
3c). 2a is thus almost 4 times as effective as 1a in quenching the
[IrIII]* luminescence. The combination of luminescence and CV
data indicated that the [IrIII]* species with a redox potential E0’ of
+1.27 V vs SCE (Table S5) could oxidize 2a (EP = 0.50 V vs SCE
with lutidine) but not 1a (EP > 1.8 V vs SCE; Figure S59 and S60,
SI). These results suggest that the initial step of the photocatalysis
involves the reductive quenching of [IrIII]* by 2a to generate the
thiophenol radical. 1a likely quenched [IrIII]* luminescence via
energy transfer.
the stability of this dual catalyst system. This work demonstrates
for the first time the ability to merge photoredox and
organometallic catalysts in MOFs to boost catalytic activities and
highlights the opportunity in designing multifunctional MOF
photocatalysts for challenging organic transformations.
Acknowledgements
We acknowledge funding from the U.S. National Science
Foundation (CHE-1464941). Y.Y.Z. acknowledges the financial
support from National Natural Science Foundation (21771049)
and China Scholarship Council. XAS analysis was performed at
Beamline 10-BM, Advanced Photon Source (APS), Argonne
National Laboratory (ANL). Use of the Advanced Photon Source,
an Office of Science User Facility operated for the U.S.
Department of Energy (DOE) Office of Science by Argonne
National Laboratory, was supported by the U.S. DOE under
Contract No. DE-AC02-06CH11357. We acknowledge Mr Wenbo
Han and Mr Zhe Li for experimental assistance.
Luminescence of the [IrIII]* species in Me2L was also effectively
quenched by (Me2DBB)NiCl2, affording a KSV(1a) value of 0.743
± 0.008 (Figure S58, SI). CVs of (Me2DBB)NiCl2 showed four
reduction peaks at −0.93, −1.28, −1.66, and −1.78 V vs SCE in
DMF (RNi,1, RNi,2, RNi,3 and RNi,4,), corresponding to the NiII/I, NiI/0,
Me2DBB0/●−, and Ni0/0●− couples, respectively.[10] Me2L showed
three pairs of peaks at +1.78, −1.03, and −1.40 V (vs. SCE in
Keywords: metal-organic frameworks • photoredox catalysis •
nickel catalysis • heterogeneous catalysis • C−S coupling
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Based on the photophysical and electrochemical data, we
propose the reaction mechanism in Figure 3e for the dual
catalysis by Zr12-Ir-Ni. This mechanism is similar to that proposed
by Oderinde et al for the homogeneous system.[9a] In this catalytic
process, the Ir-cycle and Ni-cycle are dependent on each other
via both electron and radical transfers. In Zr12-Ir-Ni, the Ir and Ni
catalytic centers are in close proximity of ~0.6 nm from each other,
which facilitates both electron and thiophenol radical transfers
from Ir to Ni centers to significantly boost its photocatalytic activity.
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C-N cross-coupling reactions using homogeneous photoredox
and transition metal dual catalysts,[12] we expect that MOFs can
provide a tunable platform to enhance the efficiency of these
catalytic systems.
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Ni cross-coupling catalysts in close proximity facilities electron
and thiophenol radical transfers from Ir to NiII centers to speed up
the catalytic cycle whereas site isolation of Ni catalysts and cavity
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Entry for the Table of Contents
COMMUNICATION
Yuan-Yuan Zhu+, Guangxu Lan+, Yingjie
Fan, Samuel S. Veroneau, Yang Song,
Daniel Micheroni, and Wenbin Lin*
Page No. – Page No.
Merging
Photoredox
and
Organometallic Catalysts in a Metal-
Organic Framework Significantly
Boosts Photocatalytic Activities
Text for Table of Contents
The incorporation of both IrIII photoredox and NiII cross-coupling catalysts into a stable Zr12 MOF affords a solid dual photocatalyst for
C−S coupling between aryl iodides and thiols. By facilitating electron and thiophenol radical transfers from Ir to Ni centers in close
proximity, the MOF photocatalyst exhibits an order of magnitude higher catalytic activity than its homogeneous counterpart.
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