A Hydrazone-Based Covalent Organic Framework as an Efficient and Reusable Photocatalyst for the Cross-Dehydrogenative Coupling Reaction of N-Aryltetrahydroisoquinolines

Article abstract of DOI:10.1002/cssc.201601702

A hydrazone-based covalent organic framework (COF) was synthesized by condensation of 2,5-dimethoxyterephthalohydrazide with 1,3,5-triformylbenzene under solvothermal conditions. The COF material exhibits excellent porosity with a BET surface area of up t

Full text of DOI:10.1002/cssc.201601702

Accepted Article
Title: A Hydrazone-based Covalent Organic Framework as an Efficient
and Reusable Photocatalyst for the Cross-Dehydrogenative
Coupling Reaction of N-Aryltetrahydroisoquinolines
Authors: qiaolin wu, Wanting Liu, Qing Su, Pengyao Ju, Bixuan Guo,
Hui Zhou, and Guanghua Li
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201601702
Link to VoR: http://dx.doi.org/10.1002/cssc.201601702
A Journal of
www.chemsuschem.org

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
A Hydrazone-based Covalent Organic Framework as an Efficient
and Reusable Photocatalyst for the Cross-Dehydrogenative
Coupling Reaction of N-Aryltetrahydroisoquinolines
Wanting Liu,[a] Qing Su,*[a,c] Pengyao Ju,[a] Bixuan Guo,[a] Hui Zhou,[a] Guanghua Li,[b] and Qiaolin Wu*[a]
A
hydrazone-based covalent organic framework (COF) was
catalyzing visible-light driven organic transformations with high
efficiency, low cost, and minimum environmental impact and
energy consumption. In order to achieve the efficient and
environmentally benign photocatalytic transformations, it is
important to develop heterogeneous catalytic systems that not
only utilize the energies to photochemically activate organic
substrates for desired synthetic transformations, but also are
easily recovered and reused in photocatalytic reactions.
synthesized by condensation of 2,5-dimethoxyterephthalohydrazide
with 1,3,5-triformylbenzene under solvothermal conditions. The COF
material exhibits excellent porosity with a BET surface area of up to
1501 m2g˗1, high crystallinity, and good thermal and chemical
stability. The COF material exhibited efficient photocatalytic activity
towards cross-dehydrogenative coupling (CDC) reactions between
tetrahydroisoquinolines and nucleophiles such as nitromethane,
acetone and phenylethyl ketone. The metal-free catalytic system
also offers attractive advantages including simplicity of operation, the
wide substrate adaptability, ambient reaction conditions and robust
recycling capability of catalyst, thus providing a promising platform
for highly efficient and reusable photocatalysis.
Covalent organic frameworks (COFs) as an emerging class of
crystalline porous materials are covalently assembled from
organic building blocks.[13] The well-defined COF materials with
periodic architectures and tailored functionalities have offered
superior potential for a variety of applications, such as gas
storage and seperation,[14] optoelectricity,[15] energy storage,[16]
proton conduction,[17] drug delivery[18] and catalysis.[19] Up to now,
a limited number of reversible reactions have been successfully
applied in the construction of a significant amount of two-
dimensional (2D) COFs and a few 3D COFs. In most cases, the
linking groups are boronates, boroxines,[20] triazines,[21] imines,[22]
or hydrazones.[23] For example, the imine-based COF-LZU1 in
combination with Pd was used as highly efficient catalyst in
Suzuki coupling reaction.[24] Moreover, the Schiff-base chemistry
or dynamic imine chemistry has been widely explored for the
synthesis of the largest amount of COFs.[25] It is worth noting
that photoactive COFs with charge separation capabilities have
also been prepared, but hardly been explored as visible light
active photocatalysts for the production of solar fuels.[26] Very
recently, the triazine based COF by condensation polymerization
between cyanuric chloride and perylene diimide has been
developed as highly efficient visible light active flexible
photocatalyst for solar fuel production from CO2.[27] These
findings also indicate that 2D COFs are organic scaffolds, which
are promising for developing photoenergy conversion and
photocatalytic systems. Therefore, it is of great importance in
constructing functional COFs for certain applications. Hydrazone
linkage offers improved hydrolytic and oxidative stability in
compared with boronate ester linkage,[28] and provides dynamic
character through the reversibility of the imino bond and
hydrogen bonding sites through the amide group. Since the
pioneering work by Yaghi,[20] the hydrazone-linked COFs have
received growing attention in view of the structural variations,
the synthetic accessibility, and reversibility, and their potential
for a variety of applications.[29] In this regard, the hydrazone-
based TFTP-COF has been reported to be the first COF to show
photocatalytic hydrogen evolution under visible light irradiation in
the presence of Pt, which is comparable with the best non-metal
photocatalysts for hydrogen generation.[30]
The development of mild, convenient and efficient synthetic
methods for the formation of C−C bonds is highly desirable in
organic synthesis. In the last few decades, the direct and
efficient transformation of C−H into C−C bonds has attracted
continuous interest because of the increasing requirements for
green and sustainable chemistry.[1] As part of these efforts, the
cross dehydrogenative coupling (CDC) reactions provide
versatile methodologies for the direct and selective construction
of C−C bonds from two different C−H bonds without the need of
substracte pre-activation.[2] To date, these direct C−H
transformations have been achieved by various catalysts,
including transition metals, organocatalysts, the combined use of
metal and organocatalysts, and enzymes. The first example of
CDC reaction with isoquinoline derivative and nitromethane
catalyzed by copper salt was reported by Li in 2005.[3] Recently,
Stephenson demonstrated an efficient method for the visible
light-mediated photocatalytic aza-Henry reaction of nitromethane
with N-aryltetrahydroisoquinolines (THIQ) using air as terminal
oxidant.[4] Considerable efforts have been devoted to the active
area, and the aza-Henry reaction of THIQ derivatives represents
one of the most exploited photocatalytic transformations using a
variety of photocatalysts, such as iridium,[5] platinum,[6] ruthenium,
[7]
organic dyes,[8] TiO2,[9] CdS,[10] metal−organic frameworks,[11]
and porous organic polymers.[12] Despite these impressive
advances, it remains
a great challenge to explore new
photocatalytic systems that are highly stable, and highly active in
[a]
W. Liu, Prof. Dr. Q. Su, P. Ju, B. Guo, H. Zhou, Prof. Dr. Q. Wu
College of Chemistryi
Jilin Universrity
2699 Qianjin Street, Changchun 130012 (China)
E-mail: suqing@jlu.edu.cn; wuql@jlu.ediiu.cn
Prof. Dr. G. Li
State Key Laboratory of Inorganic Synthesis and Preparative
Chemistry
Jilin Universrity
2699 Qianjin Street, Changchun 130012 (China)
Prof. Dr. Q. Su
State Key Laboratory of Fine Chemicals
Dalian University of Technology
Dalian 116024 (China)
[b]
[c]
With these considerations in mind, it is challenging to develop
functional COFs by bottom-up or post-synthesis strategies to
achieve light harvesting and further highlight the application of
COFs in photocatalysis. To the best of our knowlege, there are
no examples involving COFs based catalyst system for
application in photocatalytic CDC reactions. Herein, we report
the synthesis and structural characterization of new hydrazone-
based covalent organic framework (TFB-COF) through
Supporting information for this article can be found under
http://dx.doi.org/10.1002/cssc.xxxxxxxxx.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
condensation of 2,5-dimethoxyterephthalohydrazide with 1,3,5-
triformylbenzene under solvothermal conditions. The resulting
COF with large BET surface area and high crystallinity was used
as highly active photocatalyst in CDC reactions of a wide variety
of substrates at room temperature. The TFB-COF could be
readily recycled and reused for these photocatalytic
transformations without significant loss of catalytic activity.
TFB-COF was synthesized by acid catalyzed reversible
condensation
between
2,5-dimethoxyterephthalohydrazide
(DMTH) and 1,3,5-triformylbenzene (TFB) under solvothermal
conditions (Scheme 1). The resulting COF was obtained as a
pale-yellow solid with a high yield of 89%. TFB-COF was
insoluble in common organic solvents such as hexane, methanol,
acetone,
tetrahydrofuran
(THF),
toluene,
N,N-
Figure 2. 13C CP/MAS NMR spectrum of COF. The asterisks denote the
spinning sidebands. The assignments of 13C chemical of COF shifts are
indicated in the chemical structures.
dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).
Scheme 1. Schematic representation for the synthesis of TFB-COF.
The atomic precision construction of TFB-COF was further
assessed by the 13C cross-polarization/magic-angle-spinning
(CP/MAS) NMR spectroscopy and the signal assignments were
depicted in Figure 2. The peak at 161 ppm could be attributed to
the carbon atoms of the carbonyl groups. The characteristic
signal at 151 ppm was unambiguously assigned to the carbon
atoms of the the imine groups.[23] The high-field signal at 57 ppm
corresponded to the methoxy groups of the aromatic rings.
The TFB-COF was characterized by Fourier transform infrared
(FT-IR) spectroscopy (Figure 1). The FT-IR spectra of TFB-COF
showed the disappearance of aldehyde carbonyl stretching band
(1695 cm−1) of TFB and the N−H stretching band (3297 cm−1) of
DMTH, indicating the absence of starting material. Meanwhile,
the characteristic stretching bands of the imine group appeared
at 1661 cm−1 and 1237 cm−1 in the IR spectrum of TFB-COF,
which were in good agreement with those corresponding values
of reported COF materials.[23,26b]
Figure 3. Observed PXRD patterns of TFB-COF (as-synthesized, black) and
TFB-COF upon treatment in aqueous solutions for 3h (pH = 3, red; pH = 13,
blue).
The crystalline structure of TFB-COF was determined by
powder X-ray diffraction (PXRD) analysis with Cu Kα radiation
(Figure 3). The PXRD pattern exhibited an intense peak at 3.35
corresponding to the reflection from the (100) plane, which is in
line with most COFs with a hexagonal structure.[23, 31] The PXRD
patterns of TFB-COF also indicated the crystallinity of TFB-COF
is preserved after treatment in aqueous solutions with pH values
of 3 and 13 for 3 hours, displaying its remarkable stability. The
thermal
stability
of
TFB-COF
was
confirmed
by
thermogravimetric analyses (TGA). As shown in Figure S1, TFB-
COF is stable up to 375 °C.
The diffuse reflectance UV/Vis spectra of TFB-COF and its
monomers were shown in Figure 4. The diffuse reflectance
spectra reveals that TFB-COF shows an absorption edge at ca.
450 nm with an optical band gap of 2.88 eV determined by the
Kubelka˗Munk function. These values are red-shifted by 40–60
Figure 1. FT-IR spectra of TFB-COF (black), DMTH (red), and TFB (blue).
The FT-IR spectrum of COFs (black) shows a –C=N– stretch at 1661 cm-1,
indicating the successful formation of the imine bond linkages.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
measured at 77 K (Figure 5). It was found that TFB-COF show
Type IV isotherms.[34] The Brunauer−Emmett−Teller (BET)
surface area of TFB-COF was calculated to be 1501 m2g−1,
which is excellent surface area among all hydrazone based
COFs,[35] and is comparable to those of 2D COFs with
hexagonal pore systems.[31,36] High nitrogen uptakes at low
nm in comparison to the solid-state absorption spectra of the
building blocks, which could be attributed to a higher degree of
conjugation in the extended frameworks.[32] The red-shifted
absorption of the COF with respect to the monomers has been
reported for other COFs.[33] Furthermore, it indicates that the
COF catalyst has a suitable band gap for photocatalytic
reactions under visible light irradiation.
relative pressures (P/P0
< 0.1) indicate the existence of
micropores. Pore-size distribution calculated by nonlocal density
functional theory (NLDFT) method also revealed that the pores
are centered at 1.3 and 2.2 nm for TFB-COF (Figure 5),
demonstrating the presence of both micropore and mesopore in
the networks. The total pore volume of the obtained COF was
estimated to be 0.88 cm3g˗1.
To understand the morphologies of the surface of TFB-COF,
their microstructures were investigated by scanning electron
microscopy (SEM) as shown in Figure 6. The SEM image of
TFB-COF reveals the morphology composed of the large
assembly of particles. High resolution tunneling electron
microscopy (HR-TEM) also revealed the porous texture of COF
materials (Figure 6).
Figure 4. UV/Vis diffuse reflection spectra of TFB-COF and its monomers
(top), Plot of Kubelka-Munk function for the band gap determination (bottom).
Figure 6. SEM image of TFB-COF (top) and TEM image of TFB-COF (bottom).
The CDC reaction is one of the most powerful synthetic tools
for the formation of C−C bonds by oxidative coupling of two
different C−H bonds.[2] The dehydrogenative coupling reaction of
N-phenyl-1,2,3,4-tetrahydroisoquinoline with nitromethane was
initially examined using high crystallic COF as the photocatalyst.
A
number of tests were carried out using N-substituted
tetrahydroisoquinoline and CH3NO2 as the substrates in the
presence of O2 with an energy-saving lamp (45 W) as the light
source at room temperature (Table 1). The effects of different
amounts of COF catalyst were explored, and the results
indicated that the amounts of catalyst showed pronounced effect
on the reaction efficiency (Table 1, entries 1-6). We also found
that slight decrease in yield in this transformation was achieved
in air, indicating the significant role of molecular oxygen in the
CDC reaction (Table 1, entry 7). Furthermore, a lower yield of 73%
was obtained with an increase of amount of CH3NO2. The
reaction was much slower with a 24 W household energy-saving
Figure 5. Nitrogen adsorption (black symbols) and desorption (red symbols)
isotherms of TFB-COF (top). Pore size distrution of TFB-COF (bottom).
The surface area and porosities of TFB-COF were further
determined by nitrogen adsorption−desorption isotherms
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
Table 2. Reaction substrate extension of photocatalytic coupling reactions of
lamp (51% yield). The control experiments revealed that the
photocatalyst, light source and oxygen should be indispensable
for the efficient dehydrogenative coupling reaction. The
observations are consistent with those for the homogeneous
system.[4] Furthermore, Radical chain processes could be
involved in homogenous photoredox reaction systems. [37]
N-aryltetrahydroisoquinolines using TFB-COF catalyst.[a]
Table 1. Optimization of the reaction conditions of photocatalytic coupling
reaction of N-aryltetrahydroisoquinoline using TFB-COF catalyst.[a]
entry
R
H
nucleophiles
CH3NO2
CH3NO2
CH3NO2
CH3NO2
CH3NO2
yield [%][b]
87 (76)[c]
71 (62)[c]
70 (60)[c]
85 (74)[c]
84 (72)[c]
1
2
3
4
5
4-CN
4-COOEt
4-OMe
4-Me
catalyst
[mol %]
CH3NO2
[mL]
Time
[h]
yield
[%]b
entry
1
2
10
20
30
30
40
0
1
1
1
1
1
1
1
36
36
32
36
36
36
36
47
70
71
87
75
25
72
6d
H
H
CH3COCH3
C6H5COCH3
80 (70)[c]
82 (71)[c]
7 d
3
[a] Reaction conditions: 2-(4-R-phenyl)-1,2,3,4-tetrahydroisoquinoline (0.3
mmol), nucleophiles (1 mL), catalyst (30 mg, 30 mol %), r.t., O2 (1 atm),
irradiation by a 45 W energy-saving lamp. [b] The yield of product determined
by 1H NMR using 1,3,5-trimethoxybenzene (10 mol%) as an internal standard.
[c] Isolated yield. [d] L-proline (10 mol%) was added.
4
5
6
7c
30
8
30
30
1.5
1
36
36
73
51
9d
[a] Reactionl conditions: N-phenyl-1,2,3,4-tetrahydroisoquinoline (0.3 mmol),
r.t., O2 (1 atm), irradiation by
a
45
W
energy-saving lamp. [b]
Determined by 1H NMR using 1,3,5-trimethoxybenzene (10 mol%) as an
internal standard. [c] In air. [d] Irradiation by a 24 W energy-saving lamp.
Under the optimal reaction conditions, the scope of substrates
was then extensively investigated (Table 2). In the case of
aromatic-substituted tetrahydroisoquinolines with the electron-
withdrawing groups on the substituted aromatic ring, the
corresponding coupling products were obtained in satisfactory
yields (entries 2 and 3). It was observed that with electron-
donating groups on the para position of the phenyl ring of
Figure 7. PXRD patterns of TFB-COF (black), TFB-COF after the first (red)
and fourth (blue) runs of catalysis.
aromatic-substituted tetrahydroisoquinolines,
the desired
coupling products were obtained in high yields (up to 85%)
(entries 4 and 5). Furthermore, the photcatalytic CDC reaction
was applicable to oxidative Mannich reaction between N-phenyl
tetrahydroisoquinoline with CH3COCH3 and C6H5COCH3 (entries
6 and 7). In the presence of cocatalyst L-proline, the coupling
reaction proceeded smoothly to afford corresponding products in
high yields, indicating the present photocatalytic system being
an extension of the previous methodologies.[9, 38]
In conclusion,
framework (TFB-COF)
a
2D hydrazone-based covalent organic
was synthesized from 2,5-
dimethoxyterephthalohydrazide and 1,3,5-triformylbene under
solvothermal conditions. The resultant COF material exhibits
excellent porosity with a BET surface area of up to 1501 m2g-1
and high crystallinity. The new COF are stable in various
solvents, including concentrated acid and base, and are
o
thermally stable up to 375 C in air. The resulting COF was also
The recyclability and reusability of TFB-COF catalyst were
examined using N-phenyl tetrahydroisoquinoline and CH3NO2 as
substrates. The catalyst could be readily recovered by a simple
filtration method after each cycle. The recovered catalyst was
then washed with THF and CH2Cl2 to remove residual products
or unreacted substrates, and dried in vacuum overnight before
being reused. The results demonstrated the COF catalyst was
reusable up to three cycles without significant loss of catalytic
activity (Table S1), which indicated that TFB-COF could be
highly efficient and economic catalyst. In addition, the PXRD
patterns of TFB-COF after different reaction runs indicated the
crystallinity of TFB-COF was almost maitained (Figure 7),
although the intensity of the PXRD pattens was gradually
decreased.
shown to serve as highly efficient, recyclable heterogeneous
photocatalyst in cross-dehydrogenative coupling (CDC)
reactions of a wide variety of substrates at room temperature.
The high photocatalytic activity of the COF is attributed to
excellent porosity feature with high BET surface area and the
efficient light-harvesting platform in such systems. Our approach
also highlights the potential of developing photoactive COFs as
highly active photocatalysts for a variety of important organic
transformations.
Experimental Section
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
Reagents and solvents were purchased from commercial suppliers
and used without further purification as commercially available
unless otherwise indicated. Solvents were dried and distilled
following a standard procedure.
[12]
a) Z. Xie, C. Wang, K. E. DeKrafft, W. Lin, J. Am. Chem. Soc. 2011,
133, 2056; b) C. Wang, Z. Xie, K. E. DeKrafft, W. Lin, ACS Appl. Mater.
Interfaces 2012, 4, 2288; c) J. L. Wang, C. Wang, K. E. DeKrafft, W.
Lin, ACS Catal. 2012, 2, 417; d) J. X. Jiang, Y. Li, X. Wu, J. Xiao, D. J.
Adams, A. I. Cooper, Macromolecules 2013, 46, 8779.
a) X. Feng, X. Ding, D. Jiang, Chem. Soc. Rev. 2012, 41, 6010; b) S.
Ding, W. Wang, Chem. Soc. Rev. 2013, 42, 548; c) P. J. Waller, F.
Gandara, O. M. Yaghi, Acc. Chem. Res. 2015, 48, 3053.
a) S. S. Han, H. Furukawa, O. M. Yaghi, W. A. Goddard, J. Am. Chem.
Soc. 2008, 130, 11580; b) Y. Zeng, R. Zou, Z. Luo, H. Zhang, X. Yao,
X. Ma, R. Zou, Y. Zhao, J. Am. Chem. Soc. 2015, 137, 1020; c) H. Oh,
S. B. Kalidindi, Y. Um, S. Bureekaew, R. Schmid, R. A. Fischer, M.
Hirscher, Angew. Chem. Int. Ed. 2013, 52, 13219; d) H. Ma, H. Ren, S.
Meng, Z. Yan, H. Zhao, F. Sun, G. Zhu, Chem.Commun. 2013, 49,
9773.
1,3,5-Triformylbenzene (32.4 mg, 0.2 mmol) and 2,5-
dimethoxyterephthalohydrazide (76.3 mg, 0.3 mmol) were added
to a pyrex tube. To the mixture were added mesitylene (6 mL),
anhydrous dioxane (2 mL) and 6 M aqueous acetic acid (0.8 mL).
The tube was immersed in an ultrasonic bath for 10 min. The mixture
was then degassed through three freeze–pump–thaw cycles, sealed
under vacuum. After warming to room temperature, the sealed tube
was placed in an oven at 120 oC and left undisturbed for 3 days,
yielding a pale-yellow solid. The solid was isolated by filtration and
washed with anhydrous tetrahydrofuran and anhydrous acetone.
The resulting solid was dried under vacuum at 60 oC for 12 h to
afford COF as a pale-yellow powder (96.7 mg, 89 % yield).
[13]
[14]
Typical procedure for CDC reaction. COF (30 mg) and N-
phenyltetrahydroisoquinoline (62.8 mg, 0.3 mmol) were mixed in
nitromethane (1.0 mL), and the mixture was stirred in oxygen at
room temperature under a 45 W energy-saving lamp irradiation for
36 h. After the reaction was completed, the catalyst was isolated by
filtration and washed with acetone for three times. The combined
organic layers were dried, filtered and evaporated under vacuum.
1,3,5-trimethoxybenzene (5.1 mg, 0.03 mmol) was added to the
crude product (as an internal standard for NMR calibration). The
[15]
[16]
S. Wan, J. Guo, J. Kim, H. Ihee, D. Jiang, Angew. Chem. 2008, 20,
8958.
a) C. R. DeBlase, K. E. Siberstein, T. T. Truong, H. D. Abruna, W. R.
Dichtel, J. Am. Chem. Soc. 2013, 135, 16821; b) C. R. DeBlase, K.
Hernandez-Burgos, K. E. Silberstein, G. G. Rodriguez-Calero, R. P.
Bisbey, H. D. Abruna, W. R. Dichtel, ACS Nano 2015, 9, 3178.
a) S. Chandra, T. Kundu, S. Kandambeth, R. BabaRao, Y. Marathe, S.
M. Kunjir, R. Banerjee, J. Am. Chem. Soc. 2014, 136, 6570; b) H. Xu,
S. Tao, D. Jiang, Nat. Mater. 2016, 15, 722.
[17]
1
residue was used in the H NMR determination and the conversion
yield was calculated by integrating the peaks in the 1H NMR.
Purification by silica gel column chromatography (petroleum
ether/CH2Cl2 = 8/1, v/v) afforded the corresponding product.
[18]
[19]
Q. Fang, J. Wang, S. Gu, R. B. Kaspar, Z. Zhuang, J. Zheng, H. Guo,
S. Qiu, Y. Yan, J. Am. Chem. Soc. 2015, 137, 8352.
a) S. Lin, C. S. Diercks, Y. B. Zhang, N. Kornienko, E. M. Nichols, Y.
Zhao, A. R. Paris, D. Kim, P. Yang, O. M. Yaghi, C. J. Chang, Science
2015, 349, 1208; b) H. Xu, J. Gao, D. Jiang, Nat. Chem. 2015, 7, 905;
c) H. Xu, X. Chen, J. Gao, J. Lin, M. Addicoat, S. Irle, D. Jiang, Chem.
Commun. 2014, 50, 1292; d) H. Qian, C. Yang, X. Yan, Nat. Commun.
2016, 7, 12104.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 21004026) and the Excellent Young
Teachers Program of Jilin University. Q.S. and Q.W. thank the
open projects in State Key Laboratory of Fine Chemicals, Dalian
University of Technology (KF1403) and State Key Lab of
Inorganic Synthesis and Preparative Chemistry, Jilin University.
[20]
[21]
[22]
[23]
[24]
[25]
A. P. Cote, A. I. Benin, N. W. Ockwig, M. O’Keeffe, A. J. Matzger, O. M.
Yaghi, Science, 2005, 310, 1166–1170.
P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem. Int. Ed. 2008, 47,
3450.
F. J. Uribe-Romo, J. R. Hunt, H. Furukawa, C. Klock,M. O’Keeffe, O. M.
Yaghi, J. Am. Chem. Soc. 2009, 131, 4570.
F. J. Uribe-Romo, C. J. Doonan, H. Furukawa, K. Oisaki,O. M. Yaghi, J.
Am. Chem. Soc. 2011, 133, 11478.
S. Y. Ding, J. Gao, Q. Wang, Y. Zhang, W. G. Song, C. Y. Su, W.
Wang, J. Am. Chem. Soc. 2011, 133, 19816.
Keywords: COFs• cross dehydrogenative coupling (CDC) •
photocatalysts •tetrahydroisoquinolines
J. L. Segura, M. J. Mancheno, F. Zamora, Chem. Soc. Rev. 2016, 45,
5635.
[1]
W. Jones, F. Fehe, Acc. Chem. Res.1989, 22, 91; b) J. A. Labinger, J.
E. Bercaw, Nature 2002, 417, 507; c) K. Godula, D. Sames, Science
2006, 312, 67; d) R. G. Bergman, Nature 2007, 446, 391.
a) C. S. Yeung, V. M. Dong, Chem. Rev. 2011, 111, 1215; b) C. J. Li,
Acc. Chem. Res. 2009, 42, 335
[26] a) A. Nagai, X. Chen, X. Feng, X. Ding, Z. Guo, D. Jiang, Angew. Chem.
Int. Ed. 2013, 52, 3770; b) V. S. Vyas, F. Haase, L. Stegbauer, G.
Savasci, F. Podjaski,C. Ochsenfeld, B. V. Lotsch, Nat. Commun.
2015, 6, 8508.
[2]
[3]
[27]
[28]
[29]
R. K. Yadav, A. Kumar, N. J. Park, K. J. Kong, J. O. Baeg, J. Mater.
Chem. A 2016, 4, 9413.
Z. Li, C.-J. Li, J. Am. Chem. Soc. 2005, 127, 3672.
[4] A. G. Condie, J. C. Gonzꢀlez-Gꢁmez, C. R. J. Stephenson, J. Am. Chem.
Soc. 2010, 132, 1464.
L. Lanni, R. Tilford, M. Bharathy, J. Lavigne, J. Am. Chem. Soc. 2011,
133, 13975.
[5]
[6]
M. Neumann, K. Zeitler, Org. Lett. 2012, 14, 2658.
a) S. Y. Ding, M. Dong, Y. W. Wang, Y. T. Chen, H. Z. Wang, C. Y. Su,
W. Wang, J. Am. Chem. Soc. 2016, 138, 3031; b) F. J. Uribe-Romo,
C. J. Doonan, H. Furukawa, K. Oisaki, O. M. Yaghi, J. Am. Chem.
Soc. 2012, 133, 11478; c) D. N. Bunck, W. R. Dichtel, J. Am. Chem.
Soc. 2013, 135, 14952.
J. J. Zhong, Q. Y. Meng, G. X. Wang, Q. Liu, B. Chen, K. Feng, C. H.
Tung, L. Z. Wu, Chem. Eur. J. 2013, 19, 6443.
[7]
[8]
a) D. B. Freeman, L. Furst, A. G. Condie, C. R. J. Stephenson, Org. Lett.
2012, 14, 94; b) J. W. Tucker, Y. Zhang, T. F. Jamison, C. R. J.
Stephenson, Angew. Chem., Int. Ed. 2012, 51, 4144.
[30]
[31]
[32]
[33]
L. Stegbauer, K. Schwinghammer, B. V. Lotsch, Chem. Sci. 2014, 5,
2789.
a) Y. Pan, C. W. Kee, L. Chen, C. H. Tan, Green Chem. 2011, 13, 2682;
b) M. N. Gandy, C. L. Raston, K. A. Stubbs, Chem. Commun. 2015, 51,
11041; c) X. Z. Wang, Q. Y. Meng, J. J. Zhong, X. W. Gao, T. Lei, L. M.
Zhao, Z. J. Li, B. Chen, C. H. Tung, L. Z. Wu, Chem. Commun. 2015,
51, 11256; d) M. Rueping, C. Vila, T. Bootwicha, ACS Catal. 2013, 3,
1676.
Y. Zhang, X. Shen, X. Feng, H. Xia, Ying Mu, X. Liu, Chem.Commun.
2016, 52, 11088.
X. Chen, M. Addicoat, E. Jin, L. Zhai, H. Xu, N. Huang, Z. Guo, L. Liu,
S. Irle, D. Jiang, J. Am. Chem. Soc. 2015, 137, 3241.
a) S. Jin, X. Ding, X. Feng, M. Supur, K. Furukawa, S. Takahashi, M.
Addicoat, M. E. El-Khouly, T. Nakamura, S. Irle, S. Fukuzumi, A.
Nagai, D. Jiang, Angew. Chem., Int. Ed. 2013, 52, 2017; b) E. L.
Spitler, W. R. Dichtel, Nat. Chem. 2010, 2, 672; c) X. Ding, X. Feng,
A. Saeki, S. Seki, A. Nagai, D. Jiang, Chem. Commun. 2012, 48,
8952; d) X. Ding, J. Guo, X. Feng, Y. Honsho, J. Guo, S. Seki, P.
Maitarad, A. Saeki, S. Nagase, D. Jiang, Angew. Chem., Int. Ed.,
2011, 50, 1289; e) X. Ding, L. Chen, Y. Honsho, X. Feng, O.
[9]
M. Rueping, J. Zoller, D. C. Fabry, K. Poscharny, R. M. Koenigs, T. E.
Weirich, J. Mayer, Chem. Eur. J. 2012, 18, 3478.
[10]
[11]
T. Mitkina, C. Stanglmair, W. Setzer, M. Gruber, H. Kisch, B. Konig,
Org. Biomol. Chem. 2012, 10, 3556.
a) C. Wang, Z. Xie, W. Lin, J. Am. Chem. Soc. 2011, 133, 13445; b) W.
Q. Zhaie, K. E. DeKrafng, Q.Y . Li, Q. Zhang, Y. Lu, H. Lu, W. Wang,
X. Zhao, X. J. Wang, Inorg. Chem. 2016, 55, 1005.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
Saengsawang, J. Guo, A. Saeki, S. Seki, S. Irle, S. Nagase, V.
Parasuk, D. Jiang, J. Am. Chem. Soc. 2011, 133, 14510.
[34]
[35]
K. S. W. Sing, D. H. Everett, R. A. W. Haul, L. Moscou, R. A. Pierotti, J.
Rouquerol, T. Siemieniewska, Pure Appl. Chem. 1985, 57, 603.
a) X. Chen, M. Addicoat, S. Irle, A. Nagai and D. Jiang, J. Am. Chem.
Soc. 2012, 135, 546; b) S. Wan, F. Gandara, A. Asano, H. Furukawa,
A. Saeki, S. K. Dey, L. Liao, M. W. Ambrogio, Y. Y. Botros, X. Duan, S.
Seki, J. F. Stoddart and O. M. Yaghi, Chem. Mater. 2011, 23, 4094; c)
M. G. Rabbani, A. K. Sekizkardes, Z. Kahveci, T. E. Reich, R. Ding
and H.M. El-Kaderi, Chem.–Eur. J. 2013, 19, 3324; d) S. Chandra, S.
Kandambeth, B. P. Biswal, B. Lukose, S. M. Kunjir, M. Chaudhary, R.
Babarao, T. Heine and R. Banerjee, J. Am. Chem. Soc. 2013, 135,
17853; e) S. Kandambeth, D. B. Shinde, M. K. Panda, B. Lukose, T.
Heine, R. Banerjee, Angew. Chem., Int. Ed. 2013, 52, 13052.
H.-S. Xu, S.-Y. Ding, W.-K. An, H. Wu, W. Wang, J. Am. Chem. Soc.,
2016, 138, 11489.
[36]
[37]
[38]
(a) M. A. Cismesia, T. P. Yoon, Chem. Sci. 2015, 6, 5426; (b) M. Majek,
F. Filace, A. J. von Wangelin, Beilstein J. Org. Chem. 2014, 10, 981.
M. Rueping, C. Vila, R. M. Koenigs, K. Poscharny, D. C. Fabry,
Chem. Commun. 2011, 47, 2360.
This article is protected by copyright. All rights reserved.

10.1002/cssc.201601702
ChemSusChem
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Heterogeneous COF Photocatalyst:
Author(s), Corresponding Author(s)*
The hydrazone-based COF was
Page 1. – Page 6.
employed
as
highly
efficient,
recyclable
photocatalyst
dehydrogenative
heterogeneous
A Hydrazone-based Covalent
Organic Framework as an
in
coupling
cross-
(CDC)
reactions. Our approach highlights the
potential of developing photoactive
COFs as highly active photocatalysts
Efficient
and
Reusable
Photocatalyst for the Cross-
Dehydrogenative
Reaction
Coupling
for
a variety of important organic
transformations.
of
N-
Aryltetrahydroisoquinolines
This article is protected by copyright. All rights reserved.