Bifunctional Metal-Organic Layer with Organic Dyes and Iron Centers for Synergistic Photoredox Catalysis

Article abstract of DOI:10.1021/jacs.1c01083

Here we report the design of a bifunctional metal-organic layer (MOL), Hf-EY-Fe, by bridging eosin Y (EY)-capped Hf6 secondary building units (SBUs) with Fe-TPY (TPY = 4′-(4-carboxyphenyl)[2,2′:6′,2′′-terpyridine]-5,5′′-dicarboxylate) ligands. With the organic dye EY as an efficient photosensitizer and TPY-Fe(OTf)2 as the catalytic center, Hf-EY-Fe efficiently catalyzes aminotrifluoromethylation, hydroxytrifluoromethylation, and chlorotrifluoromethylation of alkenes. Hf-EY-Fe also catalyzes the synthesis of CF3-substituted derivatives of large bioactive molecules such as rotenone, estrone, and adapalene with sizes of up to 2.2 nm. The proximity between EY and iron centers and their site isolation in Hf-EY-Fe enhance catalytic activity while inhibiting their mutual deactivation, leading to high turnover numbers of up to 1840 and good recyclability of the MOL catalyst.

Full text of DOI:10.1021/jacs.1c01083

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Bifunctional Metal−Organic Layer with Organic Dyes and Iron
Centers for Synergistic Photoredox Catalysis
Yangjian Quan,# Wenjie Shi,# Yang Song, Xiaomin Jiang, Cheng Wang, and Wenbin Lin*
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ABSTRACT: Here we report the design of a bifunctional metal−organic layer (MOL), Hf-EY-Fe, by bridging eosin Y (EY)-capped
Hf6 secondary building units (SBUs) with Fe-TPY (TPY = 4′-(4-carboxyphenyl)[2,2′:6′,2′′-terpyridine]-5,5′′-dicarboxylate)
ligands. With the organic dye EY as an efficient photosensitizer and TPY-Fe(OTf)2 as the catalytic center, Hf-EY-Fe efficiently
catalyzes aminotrifluoromethylation, hydroxytrifluoromethylation, and chlorotrifluoromethylation of alkenes. Hf-EY-Fe also
catalyzes the synthesis of CF3-substituted derivatives of large bioactive molecules such as rotenone, estrone, and adapalene with sizes
of up to 2.2 nm. The proximity between EY and iron centers and their site isolation in Hf-EY-Fe enhance catalytic activity while
inhibiting their mutual deactivation, leading to high turnover numbers of up to 1840 and good recyclability of the MOL catalyst.
etal−organic frameworks (MOFs) are a class of 3D
M
porous materials built from metal-cluster second
building units (SBUs) and bridging ligands.1−15 The synthetic
tunability of both SBUs and bridging ligands has endowed
MOFs with interesting properties for many potential
applications. For example, the integration of Ir- and Ru-
based photosensitizers into MOFs has afforded photoactive
MOFs for photodynamic therapy, solar energy conversion, and
photoredox catalysis (Figure 1a).16−24 On the other hand,
nonmetal photosensitizers have recently received considerable
research interest owing to their environmental friendliness and
sustainable nature. In particular, organic dyes have been
actively explored as promising alternatives to noble-metal-
based photosensitizers in photoredox catalysis with relatively
low costs, wide availability, and good performance.25,26
However, organic dyes cannot be readily integrated into
MOFs owing to their large steric demands and typically low
symmetry. We surmised that organic dyes can be integrated
into metal−organic layers to afford novel 2D molecular
nanomaterials for photoredox catalysis.
As a monolayered version of MOFs, 2D metal−organic
layers (MOLs) are structurally regular, compositionally
tunable, and highly stable under catalytic conditions.27,28
MOLs can also be readily functionalized postsynthetically to
afford a new class of highly dispersible 2D molecular materials
with free substrate access to active sites.29−38 The 2D
morphology of MOLs can not only facilitate the integration
of typically complex organic dyes but also suppress self-
degradation of organic dyes via site-isolation, one of the major
challenges in photocatalysis with organic dyes.39 Herein we
report the design of the first bifunctional MOL, Hf-EY-Fe,
consisting of eosin Y (EY)-capped Hf6 SBUs and TPY-
Fe(OTf)2 (TPY = 4′-(4-carboxyphenyl)[2,2′:6′,2′′-terpyri-
dine]-5,5′′-dicarboxylate) ligands for synergistic photoredox
catalysis (Figure 1b). At 0.05−0.1 mol % catalyst loading, Hf-
EY-Fe competently catalyzed trifluoromethylative difunction-
alization of alkenes with turnover numbers of up to 1840. Hf-
Figure 1. (a) Schematic showing the integration of noble metal-based
photosensitizers into MOFs for photoinduced transformations. (b)
First bifunctional MOL with organic dyes and iron centers for
sustainable photoredox catalysis.
Received: January 28, 2021
Published: February 19, 2021
https://dx.doi.org/10.1021/jacs.1c01083
J. Am. Chem. Soc. 2021, 143, 3075−3080
© 2021 American Chemical Society
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Figure 2. Synthesis and characterization of Hf-EY-Fe. (a) Synthetic route to Hf-EY-Fe. (b) PXRD patterns of Hf-MOL, Hf-EY, and Hf-EY-Fe
(freshly prepared or after catalytic reaction) in comparison to the simulated pattern for the Hf6 MOL. (c, d) UV−vis (c) and fluorescence (d)
spectra of EY (black), Hf-EY (red), and Hf-EY-Fe (blue). (e−h) TEM image (e), HRTEM image (f), AFM topography (g), and height profile (h)
of Hf-EY-Fe. (i−k) Fe XPS (i), XANES spectra (j), and EXAFS fitting (k) of Hf-EY-Fe.
EY-Fe was also used for the functionalization of complex
bioactive molecules with sizes of 1.4−2.2 nm, demonstrating
substrate accessibility and versatility of the MOL catalyst.
Free-standing Hf-MOL of the composition Hf6(μ3-O)4(μ3-
OH)4(HCO2)6(TPY)2 was first synthesized via a solvothermal
reaction of HfCl4 and H3TPY in N,N-dimethylformamide
(DMF) at 120 °C using formic acid and water as modulators.40
The Hf6−SBUs in Hf-MOL are laterally bridged by TPY
ligands and vertically terminated by formate groups to afford
an infinite 2D network (Scheme S1). Transmission electron
microscopy (TEM, Figures S1a) and atomic force microscopy
(AFM, Figures S1b) imaging proved the monolayer morphol-
ogy of Hf-MOL with a thickness of ∼1.5 nm (Figures S1c).
The metathesis reaction between the formate capping
groups of Hf-MOL and EY afforded Hf-EY MOL with EY-
capped Hf6−SBUs (Figures 2a and S2). The loading of EY was
determined to be 10 mol % (relative to Hf6−SBU) by UV−vis
spectroscopy (Figure S3), leading to a formula of Hf6(μ3-
O)4(μ3-OH)4(HCO2)5.9(EY)0.1(TPY)2 for Hf-EY. The EY
loading was increased to 20 mol % in Hf-EY(H) when the
mixture of EY and Hf-MOL was heated at 90 °C for 24 h
(Figure S3). Treatment of Hf-EY with Fe(OTf)2 in CH3CN at
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room temperature gave Hf-EY-Fe with the formula of Hf6(μ3-
O)4(μ3-OH)4(HCO2)5.9(EY)0.1[TPY-Fe(OTf)2]2 (Figure 2a
and Scheme S2). The ratio of Hf to Fe was determined as
∼3:1 by inductively coupled plasma mass spectrometry (ICP-
MS), consistent with the proposed molecular formula of Hf-
EY-Fe.
TEM (Figure 2e) and AFM (Figure 2g) imaging confirmed
the monolayer morphology of Hf-EY-Fe with a thickness of
∼1.9 nm (Figure 2f). The increased thickness over Hf-MOL is
attributed to the coordination of EY to Hf6−SBUs (Figure S4).
High-resolution TEM (HRTEM) exhibited a 6-fold symmetry
(Figure 2f), consistent with the projection of Hf-EY-Fe
structure along the vertical direction. Hf-EY-Fe retained the
crystallinity of Hf-MOL as evidenced by their similar PXRD
patterns (Figure 2b). Hf-EY and Hf-EY-Fe exhibited
absorption peaks in their UV−vis spectra similar to those of
EY (Figure 2c). The luminescence spectrum of Hf-EY showed
an emission peak at ∼560 nm similar to that of EY, but this
emission peak completely disappeared in Hf-EY-Fe (Figure
2d), due to luminescence quenching of EY by the Fe(OTf)2
center in Hf-EY-Fe (Figure 3a).
(2p1/2) were assignable to the FeII species. In addition, the
extended X-ray absorption fine structure (EXAFS) feature of
iron centers in Hf-EY-Fe was well-fit to the (terpy)Fe(OTf)2
(terpy = terpyridine) structure with nearly identical coordina-
tion geometry (Figures 2k and S6).
In view of the importance of the CF3 group in small-
molecule drugs,41−46 we chose trifluoromethylative difunction-
alization of alkenes as the model reaction to evaluate the
catalytic performance of Hf-EY-Fe. Upon blue LED irradiation
at room temperature, Hf-EY-Fe (0.05−0.1 mol % based on
EY) competently catalyzed aminotrifluoromethylation, hydrox-
ytrifluoromethylation, and chlorotrifluoromethylation of al-
kenes with turnover numbers of up to 900, 850, and 1840,
respectively. Aryl alkenes bearing electron-withdrawing or
electron-donating groups underwent aminotrifluoromethyla-
tion reactions with Umemoto’s reagent and nitriles smoothly
to give corresponding products 1c−8c in good to excellent
isolated yields (Tables 1 and S2). The amination resulted from
Table 1. Hf-EY-Fe-Catalyzed Trifluoromethylative
a
Difunctionalization of Alkenes
X-ray absorption near edge structure (XANES) analysis
indicated the +2 oxidation state of iron in Hf-EY-Fe by
comparing the energy of its pre-edge peak to that of the
Fe(OTf)2 reference (Figure 2j). The Fe2+ oxidation state was
further verified by X-ray photoelectron spectroscopy (XPS). As
shown in Figure 2i, the peaks at 709.9 eV (2p3/2) and 723.3 eV
a
Reactions at 0.1 mmol scale with Hf-EY-Fe (0.05−0.1 mol % based
on EY) at room temperature, CF3-1 = Umemoto’s reagent, CF3-2 =
CF3SO2Cl. Comparation on TON among MOL catalyst, Ru-
photosensitizer47,48 and (diarylamino)anthracene organic catalyst.49
electrophilic attack on nitriles by the in situ generated carbon
cation followed by hydrolysis. In the presence of Hf-EY-Fe
(0.1 mol % based on EY), aryl alkenes reacted with
Umemoto’s reagent and water to afford CF3-substituted
alcohols 9c−14c efficiently (Tables 1 and S2). Furthermore,
Hf-EY-Fe efficiently catalyzed the chlorotrifluoromethylation
of alkenes by using CF3SO2Cl as the bifunctional agent
(Tables 1 and S2). Corresponding products 15c−17c and 20c
were obtained in 70−86% isolated yields. Long-chain alkenes
1-hexadecene and 7-bromo-1-heptene also coupled with
Figure 3. (a) Luminescence quenching of Hf-EY-Fe with different Fe
loadings. (b) Emission spectra of Hf-EY after the addition of different
amounts of CF3SO2Cl. Insets show plots of I0/I of EY as a function of
equivalents of [Fe] compound (a) or CF3SO2Cl (b). (c) Time-
dependent yields of 1c with different catalysts. (d) Yields of 19c with
recovered Hf-EY-Fe in five consecutive runs. (e) Proposed reaction
mechanism.
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CF3SO2Cl to generate 18c and 19c in 90 and 95% yields,
respectively. The reactions at 1 and 10 mmol scales afforded
19c in 92 and 90% yields, respectively.
Upon excitation at 400 nm, luminescence quenching of Hf-
EY-Fe with different Fe loadings was evaluated, with a Ksv(Fe)
̈
of 0.72 for the fitted Stern−Volmer equation (Figures 3a and
To further illustrate the synthetic utility and versatility of the
MOL catalyst, Hf-EY-Fe was used for late-stage functionaliza-
tion of bioactive molecules (Tables 1 and S2). Nootkatone (an
environmentally friendly insecticide) and rotenone (an organic
pesticide) underwent chlorotrifluoromethylation efficiently to
obtain CF3-functionalized products 21c and 22c in good
yields. The vinyl derivatives of large biomolecules including
Fmoc-phenylalanine (an essential α-amino acid), adapalene
(an effective antiacne drug), and dehydrocholic acid (a useful
hydrocholeretic) also reacted with CF3SO2Cl to give products
24c−26c in 58−80% isolated yields. In addition, the vinyl
derivative of estrone, one of three major endogenous
estrogens, was also compatible with the aminotrifluoromethy-
lation reaction to afford CF3-substituted product 23c in 56%
yield. These products exhibit large sizes ranging from 1.4 to 2.2
nm and cannot readily diffuse through the channels of 3D
MOFs (Figure S8). The successful trifluoromethylative
difunctionalization of large bioactive molecules supports the
freely accessible active sites in the MOL catalyst and its
potential applications in drug discovery and synthesis.
Hf-EY-Fe exhibits much higher TON numbers for
trifluoromethylative difunctionalization (Table 1) over Ru-
photosensitizer47,48 and (diarylamino)anthracene organic
catalyst.49 In addition, the 0.05−0.1 mol % loading of Hf-
EY-Fe (based on EY) is much lower than the typical 1−5 mol
% loading in homogeneous EY-catalyzed reactions.50 The low
catalyst loading and high TON numbers of Hf-EY-Fe may be
attributed to the proximity between EY and [Fe] centers for
facile transfer of radical intermediates and their site isolation
which prevents the deactivation and poisoning of both EY and
[Fe] centers. Hf-EY-Fe was stable under catalytic conditions as
evidenced by the maintenance of PXRD patterns in the
recoverd MOLs (Figure 2b). Furthermore, Hf-EY-Fe was
readily recovered and used in five runs of chlorotrifluor-
omethylation of 7-bromo-1-heptene without significant
decrease in product yields (Figure 3d). Interestingly, the
homogeneous control reaction using a combination of EY and
(terpy)Fe(OTf)2 did not afford aminotrifluoromethylation
product 1c (Figure 3c), likely due to the low loading (0.1
mol %) of EY and its deactivation by excess (terpy)Fe(OTf)2.
We conducted several control experiments to probe the
reaction mechanism. The replacement of Hf-EY-Fe by Hf-EY-
FeBr2, or Hf-EY in aminotrifluoromethylation of styrene gave
the target product 1c in 15 and 12% yields, respectively,
suggesting the crucial role of Fe center in the reaction
(Schemes S4 and S5). In the absence of EY, Hf−Fe MOL
catalyzed the aminotrifluoromethylation of styrene to afford 1c
in <5% yield (Scheme S6). No reaction was observed without
light radiation (Scheme S7). These results indicate the
photocatalytic nature of the synergistic catalysis. In addition,
radical capture by (2,2,6,6-tetramethylpiperidin-1-yl)oxyl
(TEMPO) completely shut down the aminotrifluoromethyla-
tion reaction, but afforded 1-trifluoromethoxy-2,2,6,6-tetrame-
thylpiperidine quantitatively (Scheme S8). This result suggests
the involvement of trifluoromethyl radical in the amino-
trifluoromethylation reaction. Furthermore, the visible-light
irradiation on/off experiment showed that chlorotrifluorome-
thylation of 7-bromo-1-heptene was completely stopped when
light was turned off and restarted when the light was turned on
(Figure S10). The results exclude the radical chain mechanism.
S9a,b). This result explains the absence of the emission peak in
the luminescence spectrum of Hf-EY-Fe but the existence of
an emission peak at ∼560 nm for Hf-EY (Figure 2d). In
addition, the luminescence of Hf-EY was quenched by the
added CF3-agent or (terpy)Fe(OTf)2 with Ksv(CF3SO2Cl) of
0.21 and Ksv[(terpy)]Fe(OTf)2] of 0.16, respectively (Figures
3b and S9c−f). The substantially different Ksv values (0.72 vs
0.16) indicate the different electron transfer rates between EY
and Fe centers in the MOL and homogeneous systems, which
may account for the much enhanced catalytic performance of
Hf-EY-Fe (Figure 3c).
On the basis of these experimental results and literature
precedents,51 we propose a possible reaction mechanism as
shown in Figure 3e. Single electron transfer from [FeII] to the
photoexcited EY in Hf-EY-Fe affords the [FeIII] species and
the strongly reducing EY radical anion, which reduces the CF3-
agent to deliver open-shell trifluoromethyl radical A and
regenerate EY. The EY photosensitizer is excited by blue LED
to restart the photocatalytic cycle. The radical addition
reaction of A to alkene generates carbon radical B, which is
subsequently oxidized by the [FeIII] center that is only ∼1.0
nm away, to give carbon cation C and regenerate the [FeII]
species to finish the metal catalytic cycle. The reaction of C
with nucleophiles delivers the trifluoromethylative difunction-
alization product. In this mechanistic scenario, the close
proximity of EY and iron sites in Hf-EY-Fe facilitates the
electron and radical transfer between the two catalytic centers,
thus enhancing the synergistic catalytic performance. The site
isolation of synergistic catalytic centers also suppresses the
potential mutual deactivation and results in high turnover
numbers of up to 1840 and good recyclability (Table 1 and
Figure 3d).
In summary, we have designed the first bifunctional MOL,
Hf-EY-Fe, containing EY as the non-noble metal photo-
sensitizer and TPY-Fe(OTf)2 as the metal catalytic center. Hf-
EY-Fe effectively catalyzed aminotrifluoromethylation, hydrox-
ytrifluoromethylation and chlorotrifluoromethylation of al-
kenes with turnover numbers of up to 900, 850, and 1840,
respectively. Hf-EY-Fe also competently catalyzed trifluor-
omethylative difunctionalization of bioactive molecules includ-
ing nootkatone, rotenone, estrone, Fmoc-phenylalanine,
adapalene, and dehydrocholic acid derivatives. The compati-
bility with large bioactive molecules (up to 2.2 nm) supports
the free accessibility of active sites and versatility of the MOL
catalyst. MOLs thus provide an excellent 2D molecular
material platform to incorporate readily available organic
dyes for sustainable photoredox transformations.
ASSOCIATED CONTENT
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* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/jacs.1c01083.
Synthesis and characterization of Hf-MOL, Hf-EY, and
Hf-EY-Fe, synergistically catalytic reactions, and mech-
anistic study (PDF)
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AUTHOR INFORMATION
■
Corresponding Author
Wenbin Lin − Department of Chemistry, The University of
Chicago, Chicago, Illinois 60637, United States;
orcid.org/0000-0001-7035-7759; Email: wenbinlin@
uchicago.edu
(7) Xiao, D. J.; Bloch, E. D.; Mason, J. A.; Queen, W. L.; Hudson, M.
R.; Planas, N.; Borycz, J.; Dzubak, A. L.; Verma, P.; Lee, K.; Bonino,
̀
F.; Crocella, V.; Yano, J.; Bordiga, S.; Truhlar, D. G.; Gagliardi, L.;
Brown, C. M.; Long, J. R. Oxidation of ethane to ethanol by N2O in a
metal−organic framework with coordinatively unsaturated iron(II)
sites. Nat. Chem. 2014, 6, 590.
Authors
Yangjian Quan − Department of Chemistry, The University of
Chicago, Chicago, Illinois 60637, United States;
orcid.org/0000-0002-6500-3152
Wenjie Shi − Department of Chemistry, The University of
Chicago, Chicago, Illinois 60637, United States; College of
Chemistry and Chemical Engineering, iCHEM, State Key
Laboratory of Physical Chemistry of Solid Surface, Xiamen
University, Xiamen 361005, PR China
Yang Song − Department of Chemistry, The University of
Chicago, Chicago, Illinois 60637, United States;
orcid.org/0000-0003-4212-8814
Xiaomin Jiang − Department of Chemistry, The University of
Chicago, Chicago, Illinois 60637, United States;
orcid.org/0000-0001-8304-4938
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Emerging Multifunctional Metal−Organic Framework Materials. Adv.
Mater. 2016, 28 (40), 8819−8860.
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Cheng Wang − College of Chemistry and Chemical
Engineering, iCHEM, State Key Laboratory of Physical
Chemistry of Solid Surface, Xiamen University, Xiamen
361005, PR China; orcid.org/0000-0002-7906-8061
Complete contact information is available at:
https://pubs.acs.org/10.1021/jacs.1c01083
(15) Wei, Y.-S.; Zhang, M.; Zou, R.; Xu, Q. Metal−Organic
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Author Contributions
#Y.Q. and W.S. contributed equally to this work.
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Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
Porous Metal−Organic Frameworks. Angew. Chem., Int. Ed. 2016, 55
(11), 3566−3579.
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works for Selective 2,2,2-Trifluoroethylation of Styrenes. J. Am. Chem.
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■
We thank Dr. Kaiyuan Ni and Dr. Guangxu Lan for
experimental help. We acknowledge the National Science
Foundation and the University of Chicago for founding
support and the MRSEC Shared User Facilities at the
University of Chicago (NSF DMR-1420709) for instrument
access. XAS analysis was performed at Beamline 10-BM,
supported by the Materials Research Collaborative Access
Team (MRCAT). Use of the Advanced Photon Source, an
Office of Science User Facility operated for the U.S. DOE
Office of Science by ANL, was supported by the U.S. DOE
under Contract No. DE-AC02-06CH11357.
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Echeverría, E.; Torres, F. E.; Zhang, J. Porphyrin-Metalation-
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