Control of Redox Events by Dye Encapsulation Applied to Light-Driven Splitting of Hydrogen Sulfide

Article abstract of DOI:10.1002/anie.201704327

Solar production of hydrogen by consuming low-value waste products is an attractive pathway that has both economic and environmental benefits. Inspired by the reactive pocket of enzymes, a synthetic platform to combine photocatalytic hydrogen evolution with sulfide oxidation in a one-pot process via control over the location of the electron-transfer steps is developed. The redox-active coordination vessel Ni-TFT, which has an octahedral pocket, encapsulates an organic dye to pre-organize for photocatalytic proton reduction via an oxidative quenching pathway using the nickel corners as catalysts, generating molecular hydrogen and the oxidized dye. The oxidized dye is displaced by a neutral dye and oxidizes sulfide once outside the pocket to give element sulfur. The overall reaction constitutes hydrogen sulfide splitting, forming molecular hydrogen and elemental sulfur, which is analogous to the water-splitting reaction.

Full text of DOI:10.1002/anie.201704327

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Control of Redox Events by Dye Encapsulation Applied to Light-
driven Splitting of Hydrogen Sulfide
Authors: Xu Jing, Yang Yang, Cheng He, Zhiduo Chang, Joost N. H.
Reek, and Chunying Duan
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201704327
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10.1002/anie.201704327
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COMMUNICATION
Control of Redox Events by Dye Encapsulation Applied to Light-
driven Splitting of Hydrogen Sulfide
Xu Jing+, Yang Yang+, Cheng He*, Zhiduo Chang, Joost N. H. Reek* and Chunying Duan*
space and outer-space of the cavity, respectively.[7]
Abstract: Producing solar hydrogen by consuming negative value
waste products represents an attractive pathway that presents both
economic and environmental benefits. Inspired by the pocket
feature of enzymes, a synthetic platform to combine photocatalytic
hydrogen evolution with sulfide oxidation in a one-pot process via
control over the location of electron transfer steps is reported in this
paper. The redox-active coordination vessel NiTFT, which exhibits
an octahedral pocket, encapsulates an organic dye to pre-organize
for photocatalytic proton reduction via an oxidative quenching
pathway using the nickel corners as catalysts, generating molecular
hydrogen and the oxidized dye. The oxidized dye is displaced by a
neutral dye and oxidizes sulfide once outside the pocket to give
element sulfur. The overall reaction constitutes hydrogen sulfide
splitting, forming molecular hydrogen and elemental sulfur, which is
analogous to the water-splitting reaction. The high efficiency, simple
An interesting application of such an approach would be the
light-driven splitting of hydrogen sulfide (H2S), as H2S is an
abundant chemical feedstock that is collected as a by-product in
the oil and gas industry. Whereas hydrogen sulfide itself has
little value, after splitting into molecular hydrogen and elemental
sulfur, the components have significant economic value. Among
the reported decomposition methods, the photochemical splitting
of H2S by combining sulfide oxidation and proton reduction using
solar energy has been postulated as an interesting sustainable
strategy.[8] However, as sulfide ions always form polysulfides
(Sn2-) when acting as electron sacrificial reagents[9] and both the
polysulfide and sulfide can coordinate strongly to a potential
transition-metal catalysts, leading to poisoning or decomposition,
so far homogeneous catalysts that can split hydrogen sulfide
separation of hydrogen gas and sulfur solid from the reaction mixture, have not been reported. Herein, we report a new strategy in
represent major advantages for potential applications.
which light-driven proton reduction is combined with sulfide
oxidation by separating both redox events in space. We created
a nickel-based octahedral pocket that encapsulates fluorescein
(FL) as a dye for light-driven hydrogen evolution inside the
cavity, whereas the oxidized dye becomes water soluble and
performs chemical oxidation outside the pocket (Scheme 1). The
overall reaction constitutes hydrogen sulfide splitting, forming
elemental sulfur and molecular hydrogen, analogous to water-
splitting reaction.
Catalytic strategies inspired by natural enzymes that work under
ambient conditions have attracted recent interests as they may
lead to important future tools for efficient chemical conversions.[1]
To achieve efficiencies and selectivities similar to that displayed
by enzyme, scientists have devised several kind of macrocycles
with well-defined pockets, in which chemical transformations can
take place.[2,3] Reactions performed in such confined spaces can
be enhanced reaction rates by the proximity effects, leading to
unusual selectivity because of the restricted rotational freedom
of substrates in the cage.[4] Recently it was demonstrated that
confinement effects can be very beneficial if the catalytic active
species is only encapsulated during a part of the catalytic
cycle.[5,6] In view of our interest to develop host-guest systems
for photo-catalytic redox reactions,[7] as encapsulation of neutral
photosensitizers into the hydrophobic pocket of a cage that after
photo-induced electron transfer to the redox center may lead to
dissociation of the oxidized dye, entails a new strategy to control
redox events in solution. Such separation of redox events may
avoid unwanted electron transfer and energy transfer processes,
and as such it could provide a new synthetic platform to combine
photocatalytic hydrogen evolution with substrate oxidation in a
one-pot process through control over the location, i.e., inner-
Scheme 1. Schematic picture of the approach using a supramolecular system
for the encapsulation of an organic dye within the cavity of the polyhedron to
combine light-driven hydrogen production with sulfide oxidation by separating
both redox events in space.
For the preparation of the new octahedral cage, we used a
tritopic ligand, 2,2,2-((nitrilotris(benzene-4,1-diyl))tris-(methanyly
lidene))-tris(hydrazinecarbothioamide), H3TFT.[10] The reaction of
Ni(CH3COO)2·4H2O with H3TFT in DMF solution gave the
octahedron NiTFT in 40% yield. The coordination of the ligands
to the metal ions in the self-assembled structure was confirmed
by the splitting and shifting of the resonance signals in the 1H-
NMR spectrum. Specifically, the disappearance of the imine
proton C(S)-NH signals at 11.38 ppm and the significant upfield
shift of the thiosemicarbazone signals indicate that the bidentate
moieties are coordinated to the nickel ions. X-ray structure
analysis revealed the formation of Ni6L4 octahedron in the solid
state.[11] The three rigidly separated NS chelators of each ligand
coordinate with three different metal centres, whereas six metal
centres occupy the corner positions of the octahedron, each is
coordinated in a distorted square planar geometry. The high
Dr. X. Jing, Prof C. He, Y. Yang, Z. Chang and Prof. C. Duan
State Key Laboratory of Fine Chemicals .
Dalian University of Technology,
Dalian, 116024, China.
Dr. X. Jing and Prof. C. Duan
Collaborative Innovation Center of Chemical Science and
Engineering(Tianjin),
Tianjin 300071, China.
E-mail:cyduan@dlut.edu.cn
Prof J. N. H. Reek
Van’t Hoff Institute for Molecular Science
University of Amsterdam,
Science Park 904, 1098 XH Amsterdam, The Netherlands
E-mail:J.N.H.Reek@uva.nl
[+] The two authors contributed equally to this work.
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/anie.201xxxxxx.
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10.1002/anie.201704327
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coordination ability of sulfur-containing chelators makes the
octahedron NiTFT very stable, and should therefore allow the
photochemical reaction to occur even in the presence of sulfide
anions. The octahedral cage possesses ideal C3 symmetry with
one of the four ligands located on the crystallographic C3 axis. A
pseudo-S4 symmetry is achieved by alternatively arranging the 4
planar ligands onto the eight triangular faces of the octahedron
defined by the six metal ions. The M6L4 cage has a similar
structure as the palladium octahedron and the nickel octahedron
previously reported by Fujita[12] and by us.[13] The geometry is
heavily distorted with an inner volume of approximately 900Å3.
The separation between the two metal ions coordinated to the
same ligand is approximately 14.7 Å, and that between two
diagonally opposing metal ions is approximately 20.6 Å. The
amine groups in the building blocks that are located within the
cavity of the pocket could act as hydrogen-bond acceptors,
which together with possible aromatic stacking interactions of
the phenyl rings may facility binding of fluorescein molecules
(FL) within the pocket of the octahedron.
luminescence lifetime similar to that of the decay of the emission
of FL (4.50 ns) (Figure S8). The fact that the emission intensity
was quenched but the lifetime of the remaining luminescence is
similar to that of the free dyes suggests that the quenching
process is due to the formation of the host-guest complex.[7a] The
titration profile of FL (10 M) in the solution was analysed with a
Hill plot, and the best fit of the profile indicates the formation of a
1:1 host-guest complex with an association constant of 5.4(
0.2)104 M-1 (Figure S10). This forms the basis to perform light-
driven redox chemistry within the redox active cage, allowing
further reactions with the oxidized dye such as sulifde oxidation.
[15]
The cyclic voltammogram of NiTFT (0.1 mM), recorded in
DMF solution, display two reduction waves related to the NiII/NiI
and NiI/Ni0 reduction process around -1.2–1.5 V(vs. Ag/AgCl),
respectively. These potentials fall well in the range for proton
reduction in aqueous media.[16] Indeed, the addition of Et3NH+
(Et3N, triethylamine) to the NiTFT solution (DMF) leads to a
new wave near the redox peak at -1.50 V that increases with
increasing acid concentration (Figure 2a), indicating that NiTFT
acts as an electro-catalyst for proton reduction.
Figure 1. Structure of the NiTFT octahedron cage showing the coordination
geometry of the nickel ions and the empty sphere (red ball) from different
directions of the octahedron. The nickel, sulfur, nitrogen and carbon atoms
have displayed in green, yellow, blue, and grey, respectively.
Figure 2. Cyclic voltammograms of NiTFT(0.1 mM) containing 0.1 M TBAPF6
(black line) in the presence of different concentrations of HNEt3Cl [0.6 mM
(green line), 1.2 mM (blue line), 1.8 mM (red line), 2.4 mM (purple line)scan
rate: 100 mV/s] (a). Emission spectra of FL (10 M) (black line) upon addition
of NiTFT up to 50.0 M(b). Light-driven hydrogen evolution of systems
containing FL (2.0 mM), and theNiTFT concentration fixed at 2.0 M (black),
4.0 M (red line)or6.0 M (blue line)andNEt3 (10% v/v)( fig c), or Na2S (0.05
M) solution (fig d) as the electron donor.
The structure of the NiTFT in solution was characterized by
ESI–MS analysis, revealing a single charged species (m/z =
2535.05) that corresponds to HNi6(TFT)4 . To further evaluate
+
the binding of the FL dye in the cage, ten equivalents of FL were
added to the cage solution, which was subjected to ESI–MS
analysis. A new, intense peak at m/z = 2867.11 was observed in
the mass spectrum of that could clearly be attributed to the
After the electrochemical proton reduction reaction was
established, we first investigated the photo-chemical proton
reduction reaction. The irradiation of a solution containing FL
(2.0 mM), NiTFT (4.0 M), and NEt3 (10% v/v) in H2O/EtOH
(1:1 v/v) solution resulted in the hydrogen generation at
pH=11.0–13.0 (Figure S13) as determined by GC, and the most
efficient hydrogen production was achieved at pH≈12.6. Control
experiments revealed that the absence of any of the individual
components led to the failure for produce hydrogen, indicating
that all three species are essential for hydrogen generation. In
addition, in the absence of light no hydrogen was formed either.
When the concentrations of FL(2.0 mM) and NEt3 (10% volume)
were fixed, the volume of hydrogen produced as a function of
the concentration of NiTFT (between 2.0 M and 6.0 M) was
linear. The initial turnover frequency was 1250 mole of hydrogen
per mole of catalyst per hour, and the turnover number reached
species HNi6(TFT)4⊃FL+.
A comparison of experimentally
obtained peak with those obtained via the simulation, based on
natural isotopic abundance, confirms the formation of this host
guest complex. The 1H-NMR spectrum of FL (0.2 mM) in the
presence of NiTFT(0.1 mM) of (Figure S6) shows significant
upfield shifts of the signals associated with the base-ring protons
of the FL, (δ = 0.15 ppm in an average), indicating that the FL
molecules are encapsulated within the -electron-rich pocket of
the NiTFT octahedron.[14]
The binding of FL in the NiTFT cage was also studied by
fluorescence. As expected, the NiTFT cage appeared to be an
efficient quencher of the excited state of FL(Figure 2b). The
addition of 50 M NiTFT to an EtOH/H2O solution of FL(10 M)
quenches approximately 80% of the emission intensity of FL.
The emission (at 525 nm) of an FL solution (10 M) containing
NiTFT (50 M) decayed in a clearly exponential fashion with a
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10.1002/anie.201704327
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25,000 per mole of NiTFT, which is the largest value reported
to date for related system with FL as photosensitizer. [17]
artificial reductant Et3N, and the calculated turnover number
reached 2600 per mole of catalyst.
The superiority of the host-guest system over other relevant
systems is attributed to the pre-organization effect of the FL in
the pocket, allowing a direct photo-induced electron transfer
(PET) process from the excited state Fl* to the redox catalyst.
The new pathway via oxidative quenching is thereby facilitated
leading to direct reduction of the catalytic active sites and the
oxidized dye guest FL+.[6] When all species are free in solution,
the pathway via reductive quenching, i.e. the quenching of the
excited state Fl* by the electron donor that is present in excess
to form unstable FL- radical anions, is predominant.[18] As such,
the preorganization leads to prolonged lifetime of the system
and this new synthetic platform allows in principle the
combination of photocatalytic hydrogen evolution with substrate
oxidation via the oxidized dye in a one-pot process.
Control experiments revealed that molecular hydrogen and
elemental sulfur did not form in the absence of the catalyst or
when the reaction was carried out in the dark. Similar to the
proton reduction reaction, the pre-organization of the dye with
NiTFT cage leads to a direct photo-induced electron transfer
from the excited state FL* to the redox catalyst (oxidative
quenching), reducing the nickel complexes of the vessel,
expelling the oxidized dye FL+ from the cage.[22] The reduced
redox vessel reduces protons to produce molecular hydrogen.
The oxidized FL+ species further oxidizes sulfide in the bulk
solution to generate solid sulphur. The cage system with Fl will
undergo the next cycle of photo excitation required for proton
reduction catalysis.
In analogy to water splitting reaction,[19] the splitting of H2S to
produce both molecular hydrogen and elemental sulfur consists
of two half reactions: proton reduction and sulfide oxidation. We
anticipated that this would particularly interesting for the current
system. The coupling of photochemical reduction of protons that
occurs via oxidative quenching of the dye to generate molecular
hydrogen with a chemical reaction that the oxidized photo-
sensitizer that oxidizes sulphide to elemental sulfur will lead to
the overall reaction of the hydrogen sulfide splitting.[20]
Figure 4. Molecular structure with the atomic-numbering scheme of NiDMT.
To confirm the importance of the cage, control experiments
were performed using mono-nuclear compound NiDMT, which
was synthesized by reacting Ni(CH3COO)2•4H2O with the ligand
HDMT.[23] The crystal structure (Figure 4) exhibited that the
ligand environment around nickel in NiDMT is similar to those
of the NiTFT cage. To a solution containing 2 mM of FL, 0.05 M
of Na2S that generated by the same procedure as previously
indicated, and 24 M Ni−DMT, that ensured the same
concentration of the nickel ions, only 0.32 mL hydrogen was
generated and no yellow precipitate was observed, under the
same reaction conditions. Luminescence titrations of FL (10 M)
quenched about 38% of the emission upon the addition of up to
0.024 mM NiDMT and gave the quenching constant (Ksv)
about 1530M-1. With the consideration of the much larger
concentration of Na2S (0.05 M) under catalysis conditions,
reduction quenching by Na2S that gives the reduced organic dye
FL- is the dominant process, the sulfide ions formed polysulfides
Figure 3.(a) Pictures showing the reaction mixture solution before irradiation
(top) and after after irradiation (bottom); (b)XRD pattern of the yellowish
powerand (c)a picture of the collected powder.
2-
Sn and no element sulfur was obtained under these conditions.
To further confirm the role of the cage and pre-organization
effect, a classic inhibition experiment was carried out by adding
a non-reactive guest, glucosamine (GLA), that competes for the
binding pocket with the dye.[13] The addition of GLA (2.0 mM)
quenched the photocatalytic H2S splitting of the Fl(2.0 mM)/Ni−
TFT(4.0 M)/Na2S(0.05 M) reaction mixture, 0.32 mL hydrogen
gas was generated and no yellow precipitate was observed.
Notably, the addition of the same amount GLA into the Fl (2.0
mM)/Ni−DMT(24.0 μM)/Na2S(0.05 M) didn't change the reaction
outcome of this experiment. The competitive inhibition behaviour
of the supramolecular system confirmed the relevance of
encapsulation of the organic dye for the overall reaction. These
experiments show the importance of the pre-organization of the
Fl and the catalysts in the NiTFT cage leading to high local
concentration of the catalyst-dye complex their by facilitating the
oxidative quenching pathway.
In a simple model reaction, H2S gas was bubbled into a
H2O/EtOH (1:5 v/v) solution containing FL (2.0 mM) and NaOH
(0.1 M) to adjust the pH value to12.6, a pH value that is most
efficient for hydrogen production for the aforementioned FL/Ni
TFT/NEt3 system, leading to a concentration of S2- of ca. 0.05 M.
The resulting solution was then used for hydrogen production
under irradiation after addition of the NiTFT octahedron. As
shown in Figure 4a, the bright yellow solution turned turbid
yellow with yellowish power and hydrogen gas formed after 24
hours of irradiation. A yellowish solid formed after further
bubbling H2S gas to adjust the pH value to 8.0, which is required
for the precipitation of elemental sulphur.[21] Powder X-ray
diffraction of the yellowish solid (ca. 1 mg) that was separated
through filtration indexed to -S that matches well with spectra
of commercial elemental sulfur. When the concentration of FL
was fixed at 2.0 mM, the volume of the hydrogen produced as a
function of NiTFT concentration (between 2.0 M and 6.0 M)
was linear, just as found in the proton reduction reaction with
In view of practical applications the current process is also
interesting as the hydrogen and solid sulfer can be collected in
separate steps. An example of a potential semi-contineous
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10.1002/anie.201704327
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COMMUNICATION
process of the splitting procedure is shown in Figure 5b.[24] H2S
is bubbled into the reactor (first reactor) generating a pH at
which elemental sulfur precipitates and can be isolated (second
reactor), after which the NaOH solution can be added to
generate the proper Na2S concentration. In the final reactor the
FL photo-sensitizer and the NiTFT catalyst can produce
molecular hydrogen via direct light irradiation which can be
easily separated from solution. The remaining solution can be
transferred to the first reactor to adjust the pH value with H2S
gas for the formation of precipitates of elemental sulfur from the
solution, and the next cycle is started. If needed, additional
photosensitizer (and sometimes a small amount of catalyst) can
[3]
[4]
a) P. Thordarson, E. J. A. Bijsterveld, A. E. Rowan, and R. J. M. Nolte,
Nature, 2003, 424, 915–8; b) Z. J. Wang, K. N. Clary, R. G. Bergman, K.
N. Raymond, F. D. Toste, Nature Chem. 2013, 5, 100–103; c) M.
Schulze, V.Kunz, P. D.Frischmann, F. Würthner,. Nat. Chem. 2016, 8,
576–583; e) a) V. Bocokić, A. Kalkan, M. Lutz, A. L. Spek, D. T. Gryko,
and J. N. H. Reek, Nat. Commun., 2013, 4, 2670.
a) M. Yoshizawa, M. Tamura and M. Fujita, Science, 2006, 312, 251-
254; b) M. J. Wiester, P. A. Ulmann, C. A. Mirkin, Angew. Chem. Int. Ed.
2011, 50, 114–137 b) Y. Kohyama, T. Murase, M. Fujita, J. Am. Chem.
Soc. 2014, 136, 2966−2969;
[5]
[6]
M. Kaphan, M. D. Levin, R. G. Bergman, K. N. Raymond, F. D. Toste,
Science 2015, 350, 1235-1238.
a) M. Frank, J. Ahrens, I. Bejenke, M. Krick, D. Schwarzer, G. H.
Clever,J. Am. Chem. Soc. 2016, 138, 8279−8287; b) D. M. Dalton, S. R.
Ellis, E. M. Nichols, R. A. Mathies, F. D. Toste, R. G. Bergman, K. N.
Raymond,J. Am. Chem. Soc. 2015, 137, 10128−10131; c) M. Porel, C.
H. Chuang, C. Burda, V. Ramamurthy, J. Am.Chem. Soc. 2012, 134,
14718−14721.
be added to maintain the efficiency of the recyclable systems.
600
[7]
[8]
[9]
a) X. Jing, C. He, Y. Yang, C. Y. Duan, J. Am. Chem. Soc. 2015,
137,3967−3974; b) L. Yang, C. He, X. Liu, J. Zhang, H. Sun,Huimin
Guo, Chem. Eur. J. 2016, 22, 5253−5260; c) A.M. Kluwer, R. Kapre, F.
Hartl, M. Lutz, A. L. Spek, A.M. Brouwer, P. W. N. M van Leeuwen, J. N.
H. Reek PNAS, 2009, 26, 10460.
a) Z. Lei, W. You, M. Liu, G. Zhou, T. Takata, M. Hara, K. Domen, C. Li,
Chem. Commun. 2003, 2142–2144; b) S. V. Tambwekar, M.
Subrahmanyam, Int. J. Hydrogen Energy 1997, 22, 959–965; c) W. G.
Ma, J. F. Han, W. Yu, D. Yang, H. Wang, X. Zong, C. Li, ACS Catal.
2016, 6, 6198−6206.
400
200
0
Ni-TFT Ni-TFT/GLA Ni-DMT Ni-DMT/GLA
Photocatalysis Systems
Figure 5. (a) Turnover number of hydrogen( per Ni atom, cyan bars) and
sulphur(per Ni atom, pink bars)produced of systems containing FL(2.0 mM)/
Na2S (0.05 M) with NiTFT(4.0 M) and NiDMT (24 M) in the absence and
presence of GLA (2.0 mM). (b) Schematic picture of the recyclability of the
system via continuous bubbling of H2S gas and the addition of a dyes to
obtain molecular hydrogen and elemental sulfur under irradiation..
a) F. Bedoya-Lora, A. Hankin, G. H. Kelsall, Electrochem. Commun.
2016, 68, 19-22; b) X. Zong, J. Han, B. Seger, H. Chen, G. Lu, C. Li, L.
Wang. Angew. Chem. Int. Ed. 2014, 53, 4399–4403; c) J. Zaman, A.
Chakma, Fuel Process.Technol.1995, 41, 159–198.
[10] T. Mallegol, S. Gmouh, M. Meziane, M. Blanchard-Desce, O. Mongin,
Synthesis, 2005, 11, 1771–1774.
In summary, a new synthetic platform to combine the photo-
catalytic hydrogen evolution and sulfide oxidation in a one-pot
procedure was developed via control the host-guest location of
the redox events. The encapsulation of organic dye within the
pocket of the redox active vessel modified photocatalytic proton
reduction in the inner space of the pocket to get the molecular
hydrogen and oxidized dye. The oxidized dye gets out of the
pocket via equilibrium-controlled host-guest interaction and
causes sulfide oxidation outside the cavity to give element sulfur,
further completing the overall formation of molecular hydrogen
and elemental sulfur, analogous to the water-splitting reaction.
The simple separation of the molecular hydrogen and elemental
sulphur from solution makes this system interesting compared to
other photocatalytic systems. It provides an easy implementation
for potential practical applications in the chemical industry.
[11] Data for Ni−TFT C154H236N58Ni6O27S12, Mr = 4068.99, Hexagonal, space
group R3, dark-red block, a = 22.521(1) Å, c = 47.501(5) Å, V =20865(3)
Å3, Z = 3, Dc= 0.971 g cm-3, T = 180(2)K, μ(Mo-Kα) = 0.543mm-1. [Rint=
0.1095]. For 16290 unique reflects, final R1[with I >2σ(I)] =0.0796, wR2
(all data) = 0.1826, GOOF = 1.030. CCDC No. 1439166.
[12] M. Fujita, D. Oguro, M. Miyazawa, H. Oka, K. Yamaguchi, K.
Ogura,Nature. 1995, 378, 469–471.
[13] C. He, Z. Lin, Z. He, C. Y. Duan, C. H. Xu, Z. M. Wang, C. H. Yan,
Angew. Chem. Int. Ed. 2008, 47, 877-881.
[14] S. M. Biros, R. M. Yeh, K. N. Raymond, Angew. Chem. Int. Ed. 2008,
47, 6062–6064.
[15] B. Ginovska-Pangovska, A. Dutta, M. L. Reback, J. C. Linehan, W. J.
Shaw, Acc. Chem. Res. 2014, 47, 2621−2630.
[16] A. L. Cour, M. Findeisen, A. Hazell, R. Hazell, G. Zdobinsky, J. Chem.
Soc. Dalton Trans., 1997, 121–128
[17] Z. Han, L. Shen, W. W. Brennessel, P. LHolland, R. Eisenberg, J. Am.
Chem. Soc.2013, 135, 14659−14669.
[18] Z. Han, W. R. McNamara, M. S. Eum, P. L. Holland, R. Eisenberg,
Angew. Chem. Int. Ed. 2012, 51, 1667−1670
[19] S. Fukuzumi, T. Kishi , H. Kotani, Y.-M. Lee, W. Nam, Nat. Chem. 2011,
3, 38−41.
[20] a) M. A. Plummer, P. M. Beazley, Conversion of hydrogen sulfide to
sulfur and hydrogen. United States Patent. 1986, NO. 4592905; .b) H.
Shiina, M. Oya, K. Yamashita, A. Miyoshi, H. Matsui. J. Phys. Chem.
1996,100, 2136−2140.
Acknowledgements This study was supported by NSFC
(21421005, 21531001 and 21501041) and CPSF (No. 2016 M
590195).
[21] K. Petrov, S. Srinivasan, Int. J. Hydrogen Energy, 1996, 21,163-169.
[22] H. F. M. Nelissen, M. Kercher, L. De Cola, M. C. Feiters, R. J. M. Nolte.
Chem. Eur. J. 2002, 8, 540754
Keywords:Metal-organic Vessel •Hydrogen sulphide splitting
• Photocatalytic hydrogen generation• Supramolecular catalysis
[23] S. Chandra, S. Goel, S. D. Dwivedi, Int. J. Appl. Bio. & Pharm. Tech.
2012, 3, 149-159. Data for Ni−DMT: C20H26N8NiS2, Mr = 501.32, Mono-
clinic, space group P21/c, a = 10.409(1) Å, b = 7.442(1) Å, c =15.388(1)
Å, V = 1139.3(1) Å3, Z = 2, Dc = 1.461 g cm-3, μ(Mo-Kα) = 1.060 mm-1.
[Rint= 0.0204]. For 2011 unique reflects, finalR1 [with I >2σ(I)] = 0.0329,
wR2(all data) = 0.0981, GOOF = 1.045.CCDC No. 1439165.
[24] H. Huang,Y. Yu, K. H. Chung,Energy Fuels.2009, 23, 4420–4425.
[1]
[2]
a) M. Hoarau, C. Hureau, E. Gras, P. Faller, Coord. Chem. Rev. 2016,
308, 445–459; b) K. J. Young, B. J. Brennan, R. Tagore, and G. W.
Brudvig, Acc. Chem. Res.2015, 48, 567−574; c)T. Hisatomi, J. Kubota,
K. Domen, Chem. Soc. Rev., 2014, 43, 7520–7535.d) M. G. Walter, E.
L. Warren, J. R. McKone, S. W. Boettcher, Q. Mi, E. A. Santori, N. S.
Lewis, Chem. Rev. 2010, 110, 6446−6446;
For reviews see : a) S. H. A. M. Leenders, R. Gramage-Doria, B. de
Bruin, and J. N. H. Reek, Chem. Soc. Rev., 2015, 44, 433–48; b) M.
Raynal, P. Ballester, A. Vidal-Ferran, P.W.N.M. van Leeuwen, Chem.
Soc. Rev., 2014, 43, 1734-87; c) M. Yoshizawa, J. K. Klosterman, M.
Fujita, Angew. Chem. Int. Ed., 2009, 48, 3418–3438; d) T. R. Cook, V.
Vajpayee, M. H. Lee, P. J. Stang, K. W. Chi, Acc. Chem. Res. 2013, 46,
2464–2474; e) M. D. Ward,P. R. Raithby, Chem. Soc. Rev. 2013, 42,
1619–1636. f) J. Meeuwissen, J. N. H. Reek, Nat. Chem. 2010, 2, 615.
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10.1002/anie.201704327
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Xu Jing, Yang Yang, Cheng He, Zhiduo
Chang,Joost N. H. Reek, and Chunying
Duan
Text for Table of Contents
A supramolecular cage that allows to
combine
a photocatalytic hydrogen
evolution with sulfide oxidation in a
one-pot process was developed, by
preorganization of the dye controlling
the crucial electron transfer steps. The
overall lloop constitutes hydrogen
sulfide splitting, forming molecular
hydrogen and elemental sulfur, which
is analogous to the water-splitting
reaction.
Page No. – Page No.
Control of Redox Events by Dye
Encapsulation Applied to Light-driven
Splitting of Hydrogen Sulfide
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