Bis-Anthracene Fused Porphyrin as an Efficient Photocatalyst: Facile Synthesis and Visible-Light-Driven Oxidative Coupling of Amines

Article abstract of DOI:10.1002/chem.202003398

Development of high-performance photocatalysts for the conversion of amines is of great importance, but has remained a challenging task. Here, a bis-anthracene fused porphyrin (AFP) was synthesized in a high yield by a facile synthetic protocol, which involves a Suzuki coupling for the conjugation of two anthracene groups with a porphyrin ring, followed by oxidative cyclodehydrogenation. When serving as a photocatalyst, AFP exhibits an outstanding photocatalytic performance for the visible-light-induced aerobic oxidation of amines to imines at ambient conditions. Density functional theory calculations revealed that the low energy band gap, caused by the large planar and π-extended porphyrin structure of AFP, contributed to its high photocatalytic performance.

Full text of DOI:10.1002/chem.202003398

Accepted Article
Accepted Article
Title: Bis-Anthracene Fused Porphyrin as An Efficient Photocatalyst:
Facile Synthesis and Visible-Light-Driven Oxidative Coupling of
Amines
Authors: Pengfei Zhang, Chunyang Yu, Yucheng Yin, Jörn Droste,
Sina Klabunde, Michael Ryan Hansen, and Yiyong Mai
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: Chem. Eur. J. 10.1002/chem.202003398
Link to VoR: https://doi.org/10.1002/chem.202003398
01/2020

10.1002/chem.202003398
Chemistry - A European Journal
DOI: 10.1002/((please add manuscript number))
Article type: Article
Bis-Anthracene Fused Porphyrin as An Efficient Photocatalyst: Facile
Synthesis and Visible-Light-Driven Oxidative Coupling of Amines
Pengfei Zhanga, Chunyang Yua, Yucheng Yina, Jörn Droste,b Sina Klabundeb, Michael
Ryan Hansenb, and Yiyong Maia*
P. Zhang, C. Yu, Y, Yin, Prof. Y. Mai
School of Chemistry and Chemical Engineering, Frontiers Science Center for
Transformative Molecules, Shanghai Key Laboratory of Electrical Insulation and
Thermal Ageing, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai
200240, China
E-mail: mai@sjtu.edu.cn
J. Droste, S. Klabunde, Prof. M. R. Hansen
Institute of Physical Chemistry, Westfälische Wilhelms-Universität Münster,
Corrensstr. 28/30, D-48149 Münster, Germany
Keywords: cyclodehydrogenation, -extended porphyrin, energy bandgap, oxidation of
amines, photocatalysis
Abstract: Development of high-performance photocatalysts for the conversion of
amines is of great importance, but has remained a challenging task. Here, a bis-
anthracene fused porphyrin (AFP) was synthesized in a high yield via a facile synthetic
protocol, which involves a Suzuki coupling for the conjugation of two anthracene
groups with a porphyrin ring, followed by oxidative cyclodehydrogenation. When
serving as a photocatalyst, AFP exhibits outstanding photocatalytic performance for the
visible-light-induced aerobic oxidation of amines to imines at ambient conditions.
Density functional theory calculations revealed that the low energy bandgap, caused by
the large planar and π-extended porphyrin structure of AFP, contributed to its high
photocatalytic performance.
1
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
1. Introduction
Porphyrin macrocylic compounds are important building blocks in diverse
applications[1]. In particular, π-extended porphyrins have attracted enormous scientific
interest because of their unique optical and electronic properties[2], making them
desirable candidates for a variety of applications, such as nonlinear optical materials[3],
organic semiconductors[4], photodynamic therapy and photocatalysts[5,21a]. To synthesize
π-extended porphyrins, various types of aromatic hydrocarbons have been fused to the
meso- and β-positions of porphyrin [6]. Notably, the structure of anthracene matches
well with the geometry of the porphyrin ring (see Scheme S1 for the reported
anthacene-fused porphyrins) [7,5b] and their conjugation may generate highly delocalized
π-systems with red-shifted absorption in the visible light region, which is conducive to
photocatalytic reactions[8].
As an important building block for the synthesis of various pharmaceuticals[9] and
nanomaterials such as covalent organic framework (COFs)[10], imines and their
synthetic methods have attracted much attention. In the past few years, oxidative
coupling of amines has proven as an effective synthetic approach towards imines, which
shows advantages in high atom economy and environmental friendliness. An increasing
number of catalytic systems have been developed for this method, including metal[11]
,
photocatalysts[12], biomimetic catalysts[13], polyaniline[14], and azobisisobutyronitrile
(AIBN)[15]. Among these catalytic systems, photocatalysts[16] that use visible light as the
driving force and oxygen/air as oxidants show incomparable advantages in green
chemistry and high atomic efficiency. Various photocatalytic systems have been
developed recently, such as Nb2O512c, carbon nitride12d, graphite oxide16c and MoSx-
doped hollow carbon dots16d. The structural information and catalytic performance of
some state of the art photocatalysts for oxidative coupling of amines are summarized in
2
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Table S1 in the Supporting Information (SI). Although great progress has been made,
these catalysts suffer from a number of intrinsic problems, including either their ill-
defined structures[12d,16c,16g], their complicated and time-consuming multi-step synthetic
o
procedures[16e], or high reaction temperature requirement (usually >100 C)[16c,16d]
.
Thus, the development of an efficient visible-light-driven photocatalyst excluding these
problems is highly desirable.
Herein, we demonstrate a facile synthesis of bis-anthracene fused porphyrins (AFP),
which involves a condensation reaction and a Suzuki coupling for the conjugation of
two anthracene groups with
a
porphyrin ring, followed by oxidative
cyclodehydrogenation (Scheme 1). The resulting well-defined AFP shows a strong
absorption at 565 nm in the visible light region along with a near-infrared (NIR)
absorption ranging from 850 to 1150 nm. Cyclic voltammetry (CV) measurement
reveals reversible one-electron oxidation characteristics of AFP with a low
electrochemical gap (1.27 eV), which is close to its optical bandgap (1.11 eV). Serving
as a photocatalyst for the visible-light-induced aerobic oxidation of amines to imines,
only 0.05 mol% addition of AFP may result in >85% high yields at ambient conditions
within only 1 hour reaction time. This photocatalytic performance, including the small
amount of catalyst dosage, short reaction time, and mild reaction conditions, is
apparently superior to those of the commercial and most reported photocatalysts.
Density functional theory (DFT) calculations reveal that the high photocatalytic activity
profits from the planar and π-extended porphyrin structure of AFP, which lowers its
HOMO-LUMO bandgap. Thus, this study opens a new avenue for chemical synthesis
of high-performance visible-light-driven photocatalysts for organic chemical conversion
and affords new insight into their efficient catalytic mechanism.
3
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
2. Results and discussion
Synthesis and characterizations of photocatalyst AFP
Scheme 1. Synthesis of the photocatalyst AFP.
The synthetic route towards AFP is shown in Scheme 1 (experimental details and
characterizations are given in Supporting Information (SI), Figures S1-S17). The
alkyl porphyrin 1 was synthesized by a condensation reaction[17], followed by direct
insertion of nickel(II) ion into the porphyrin core[17], which saved a procedure of metal
exchange reaction[7] from Zn(II) to Ni(II) (see Scheme S2 for the comparison). It should
be mentioned here that it was necessary to incorporate a Ni(II) ion into the porphyrin
ring, as we found that the subsequent cyclodehydrogenation of the free-base porphyrin
ring with the anthracene groups could not be achieved. A subsequent bromination step
afforded 2 in a high yield of 96%, which was characterized by solid-state nuclear magic
angle spinning (MAS) magnetic resonance (NMR) experiments (see Figures S9 and
S10). These experiments confirmed the chemical structure of 2. Square planar
4
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
complexes of 2 with Ni(II) ions (d8) are not detectable by liquid-state electron
paramagnetic resonance (EPR) spectroscopy because of their low-spin configuration.
Only Ni(II) ions in a high-spin configuration can be detected by EPR spectroscopy. This
suggests that the broad EPR signal at g = 2.377 (see Figure S12) is due to a breaking of
the square-planar symmetry, e.g., that a square pyramidal or an octahedral complex is
created through adduct formation[18]. Additionally, a small contribution from free
porphyrin radicals[19] was visible, giving rise to a sharp EPR signal (g = 2.0031) and a
1H resonance at -7 ppm in the 1H MAS NMR spectrum (Figure S9a). Afterwards,
compound 2 was subjected to a Suzuki coupling with 9-Anthraceneboronic acid to
produce bisanthracene porphyrin Ni(II) (BAP) in a high yield of 78%. Finally, AFP was
obtained in a high yield of 97 % by cyclodehydrogenation of BAP via the Scholl
reaction using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and a catalytic
amount of triflic acid as catalyst. This reaction system was found to be much more
efficient than employing FeCl3 and AgOTf /DDQ as the catalysts, which suffered from
more complicated steps and a low yield of only 11%[7].
The resultant BAP was characterized by liquid-state NMR spectroscopy and high-
resolution matrix-assisted laser desorption/ionization time-of-flight mass spectrometry
(MALDI-TOF MS) (Figure 1, Figures S13, S14 and S15). The 1H NMR spectrum of the
precursor BAP (Figure S13) shows the presence of the doublets at 9.48 ppm and 7.80
ppm, which are assigned to β-H1 and β-H2 of porphyrin, respectively, due to their
different positions near the anthracene. The singlet at 8.48 ppm and the triplet at 0.85
ppm are assigned to anthracenyl-H7 and -CH3, respectively. The characteristic peaks
attributed to both the anthracene part and alkyl carbons are also found in the 13C NMR
(Figure S14), which confirms the successful synthesis of BAP. Moreover, MALDI-TOF
MS spectrum of BAP (Figure 1a) displays an intense signal at m/z = 1026.5056, in
5
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Figure 1. Characterizations of AFP and BAP. a) MALDI-TOF MS spectra of AFP and
BAP. b) Experimental FT-IR spectrum of AFP compared with the calculated spectrum
from DFT. Characteristic features of AFP are marked with arrows (see Table S1 and
Figure S1 for details). c) Raman spectrum of AFP. d) UV-vis-NIR absorption spectra of
AFP and BAP in THF at room temperature, the concentrations of AFP and BAP are
1.0×10-6 M.
good agreement with the calculated molar mass of 1026.5110, further confirming the
successful formation of BAP. The MALDI-TOF MS analysis also reveal a signal at m/z
= 1018.4376 for AFP (Figure 1a), in accordance with the calculated molecular mass of
1018.4484, indicative of a complete cyclodehydrogenation of BAP to AFP. Moreover,
1
taking advantage of the different H relaxation times for AFP, it was possible to
1
perform a H signal assignment (Figures S9 and S10) and a subsequent deconvolution
1
of the H MAS NMR spectrum for AFP showed good agreement with the chemical
structure. We note that only the free porphyrin radical part of AFP was visible in EPR
(g = 2.0034), which is in agreement with the larger conjugation of AFP compared to 2
(see SI for details). Figure 1b shows the experimental Fourier Transform Infrared
(FTIR) spectrum of AFP along with the calculated spectrum from DFT (see SI for
6
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
details, Table S2). The agreement of most signals in the experimental and calculated
spectra further supports the successful synthesis of AFP. Furthermore, the Raman
spectrum of AFP shows two distinct peaks at 1340 and 1590 cm-1, corresponding to the
D and G bands (Figure 1c), confirming the graphitization of BAP to AFP.
Optical and electrical properties of photocatalyst AFP
UV-vis-NIR spectrum of BAP in tetrahydrofuran (THF) exhibit intense absorption
peaks at 410 and 560 nm (Figure 1d), which could be assigned to the Soret and Q bands
of the nickel(II) porphyrin core, respectively[17]. The expansion of the π-system by
fusion with two anthracene units greatly affects the electronic structure of the nickel(II)
porphyrin. As a result, the absorption of AFP shows a large red shift with one
maximum absorption at 565 nm and another NIR band ranging from 850 to 1150 nm.
The extinction coefficient of AFP (εmax=1.45 × 105 M-1 cm-1, based on λmax=560 nm) is
slightly lower than that of BAP (εmax =2.0× 105 M-1 cm-1, based on λmax=410 nm), which
is probably a result of the stronger π-π interaction between AFP molecules compared
with that of BAP. The optical bandgaps of AFP and BAP, 1.10 and 1.90 eV, are
obtained based on their UV-vis-NIR absorption peaks in the range of 1000-1150 nm
and 550-650 nm, respectively. Fluorescence of both BAP and AFP was completely
quenched, most probably due to of the presence of the Ni2+ ion[2c]. Cyclic voltammetry
was carried out to determine the redox potentials of BAP and AFP (Figures S18 and
Table S3). BAP displays a electrochemical bandgap of 2.09 eV (equal to 2.93 V
(NHE)), close to the typical value of porphyrin[6,7]. In sharp contrast, AFP exhibits a
significantly decreased redox potential of 1.27 eV (equal to 2.11 V (NHE)). Note that
both electrochemical bandgaps are close to the optical bandgaps of BAP and AFP.
Furthermore, we measured the plot of photocurrent density versus time for AFP (Figure
S19). Obviously, after 800 seconds a relatively stable photocurrent signal with dark-
7
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
light cycles is observed for AFP, suggesting its potential applications in the field of
photocatalysts.
Photocatalytic oxidative coupling of benzylamine by AFP
Considering the visible light absorption and reversible one-electron oxidation
feature of AFP, we applied AFP as a photocatalyst for organic synthesis of imines with
BAP as a control experiment. Benzylamine compounds have high physiological and
pharmacological activities, which are widely used in the development of antibacterial
drugs[9c], we thus chose benzylamines as prominent substrates. The results of the
selected control experiments and the optimal reaction conditions for the oxidation of
benzylamines are listed in Table 1.
Although both AFP and BAP show catalytic activity, AFP exhibits much better
photocatalytic performance typically with aconversion yield of 80 % higher than that
resulted from BAP (60%, Table 1), which can be attributed to the red-shifted UV-vis-
NIR absorption and the molecular planarity of AFP[17c]. No reactions occurred in the
absence of AFP, O2 or visible light (Table 1, entries 3-5), indicating that the reactions
require the aerobic oxidation of amines into imines upon visible light irradiation.
Compared with commercial photocatalysts for the synthesis of imines, such as
tetraphenyl porphyrin (Table 1, entry 6), methylene blue (Table 1, entry 7) and
Ru(bpy)3Cl2·6H2O (Table 1, entry 8), which resulted in the yields of 57%, 40%, 72%,
respectively, AFP showed much better catalytic activity with an apparent higher
conversion yield. Furthermore, we found that the nature of solvent plays a critical role
in the present reaction (Table 1, entries 9-13); the best result was obtained in THF
(95%，Table 1, entry 11), which can be ascribed to the better solubility of both the
catalyst and the substrate in THF as well as the effect of the solvent polarity on the life
8
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
1
of O2[20]. To further study the catalytic performance of AFP, we changed the reaction
conditions, by replacing pure oxygen atmosphere with an air atmosphere while using a
9 W LED irradiation, or employing a smaller dosage of AFP. We found that the yield
did not change significantly, demonstrating that AFP is a highly effective photocatalyst
for the present synthesis of imines under oxygen and air atmospheres.
Table 1. Photocatalytic oxidative coupling of benzylamine by using different catalysts
under different conditions.a
Entry
Photocatalyst
Solvent
Oxidant
Yield(%) b
1
2
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
Toluene
CH2Cl2
THF
O2
O2
O2
N2
O2
O2
O2
O2
O2
O2
O2
O2
O2
Air
Air
Air
60
80
BAP
AFP
3
NR
NR
NR
57
4
5 c
AFP
AFP
6
Tetraphenyl Porphyrin
7
Methylene Blue
40
8
Ru(bpy)3Cl2·6H2O
72
9 d
10 d
11 d
12 d
13 d
14
15 e
16 e,f
45
AFP
AFP
AFP
AFP
AFP
AFP
AFP
AFP
63
95
CH3CN
DMF
10
trace
93
THF
THF
91
THF
85
a Reaction conditions: phenylmethanaminene (0.5 mmol), photocatalyst (0.05 mol %),
b
solvent (5 mL), irradiation of a 18 W white LED at room temperature for 1 hour.
Isolated yield. In darkness. d The benzylamine has good solubility in all the employed
c
solvents, the order of the solubility of AFP in solvents (good to poor):
THF>CH2Cl2>Toluene>CH3CN>DMF, AFP dissolved completely in THF, CH2Cl2 and
Toluene, but partly dissolved in CH3CN and DMF. e Irradiation using a 9 W white LED.
fPhotocatalyst (0.01 mol %). NR: No reaction.
Remarkably, under the optimal conditions (Table 1, entry 15), a complete
conversion of benzylamine into N-benzylidene benzylamine was realized in 1 hour
9
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
under air atmosphere with a 9 W white LED. We then examined the substrate scope of
amines, under the conditions as following: 4 or 5 (0.5 mmol) and AFP (0.05 mol %) in
THF (5 mL) were irradiated under a 9 W white LED at room temperature for 1 hour.
Then the products were purified by silica gel column chromatography (n-
hexane/dichloromethane= 4:1) to give the imine compounds 6 (Scheme 2). In general,
benzylamine with electrondonating groups such as 4-methoxy or 4-tert-butyl gave the
corresponding products in high yields of >90% (6b and 6h), while those with electron-
withdrawing groups such as 4-F or 4-CF3 gave the corresponding products in slightly
lower yields (6c and 6g). Benzylamines substituted with halogen, which could be
further functionalized, also generated the corresponding products in high yields (6c, 6d,
6e and 6f). The reactions of sterically hampered benzylamines, such as o-methoxy, o-
trifluoromethyl benzylamines, also proceeded smoothly (6i and 6j). Electron-rich
heterocyclic amines containing sulfur and nitrogen atoms, which usually poison most
metal catalysts[21], including 2-thiophenemethylamine, 3-thiophenemethylamine and
(1H-indol-2-yl)methanamine, also reacted efficiently to give products in high yields
of > 90% (6k, 6l and 6m). Furthermore, electron-deficient heterocyclic amine canalso
be converted into the corresponding imines in high yields. On the other hand, attempts
were made to oxidize simple aliphatic amines such as cyclohexylmethanamine and N-
hexylamine, but only low yields were obtained (6o and 6p), which can probably be
ascribed to the instability of the intermediate aldehyde[16e]. Finally, it is noted that for
secondary amines (5 and dihexylamine), aromatic amines were obtained in relative
lower yields (65% vs 90%) compared to 6a under the similar conditions. However,
given a reaction time (2 hours), the yields could rise to 90%, indicating that the
formation of the intermediate aldehyde is likely a key for this reaction[16e]. The chemical
nature of AFP after the catalytic reaction was tested by MALDI-TOF mass and FT-IR
10
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Scheme 2. Scope of substrates: oxidation of arylamines a
a Reaction conditions: Benzylamine 4 (0.5 mmol), catalyst AFP (0.05 mol %), THF (5
mL), irradiation under a 9 W white LED and atmosphere at room temperature for 1
hour. b Secondary amine 5 or dihexylamine were used. c Reaction time was 2 hours.
nature of AFP after the catalytic reaction was tested by MALDI-TOF mass and FT-IR
analyses (Figures S16 and S17). No obvious alteration in the characteristic peaks of the
11
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
mass and FT-IR spectra indicates the excellent chemical stability of AFP during the
catalytic reaction.
Mechanism explanation and theoretical calculation
In terms of the reported catalytic pathway of the amine-to-imine conversion
(Figure 2a)[12,16], the production of reactive oxygen, which is initiated by the
photocatalyst, is the key step to the reaction. In the catalytic process, the formation of
the excited states S1 and T1 for the photocatalyst is the prerequisite to produce reactive
oxygen, which is determined by the energy bandgap between the ground and excited
states. In our work, both the UV-vis spectra and the CV data have demonstrated that the
energy bandgap for AFP is narrower than that for BAP, favoring for the improved
photocatalytic activity of AFP. To further understand the remarkable catalytic
performance of AFP from the molecular structure point of view, quantum chemical
calculations were performed based on density functional theory (DFT). As shown in the
calculated orbital diagrams of AFP and BAP (Figure 2b), the electronic distribution for
the highest occupied and the lowest unoccupied molecular orbitals (HOMO and
LUMO) are quite different. In BAP, the π-electrons are mostly confined within the
anthracene domain in the HOMO state, whereas the π-electrons of the LUMO state are
widely distributed in both the anthracene domain and the porphyrin core. In contrast, the
π-electrons in AFP are distributed over the whole planar molecule in both the HOMO
and LUMO states with slight difference on the anthracene ring periphery, due to the
larger conjugated system extended by the fused anthracene (Figure S20). Moreover, the
energy bandgap from the ground to excited state of AFP obtained by time-dependent
DFT (TDDFT) calculation is 2.01 eV (see details in Page S20), which is lower than
•―
2.38 eV of BAP. This calculation indicates the O2 formation upon visible-light
irradiation is more favored for AFP [16e]. As a line of evidence, electron spin resonance
12
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
(ESR) spectrum demonstrates the formation of O2•―, which was trapped by 5,5-
dimethyl-1-pyrroline N-oxide (DMPO) (Figure S21). Thus, the planar molecular
structure of AFP may also help to increase the efficiency of the intersystem crossing
(the S1 to T1 energy transfer process in Figure 2a)[17c,22], which is beneficial for the
1
•―
1
generation of O2. Therefore, the preferred generation of both O2 and O2 favors the
amine-to-imine conversion[16e], which in combination with the red-shifted absorption
to the visible light region, makes AFP a highly efficient photocatalyst for the synthesis
of imines.
Figure 2. (a) Suggested reaction pathways of oxidative coupling of primary amines to
imines through photocatalysis[16e]. (b) HOMO/LUMO diagrams (B3LYP/Genecp) for
BAP (top) and AFP (bottom).
3. Conclusion
In summary, we have reported the simple synthesis of AFP, which displayed
extensive absorption in the visible light and near-IR region due to the planar and π-
extended porphyrin structure. Serving as a photocatalyst for the visible-light-induced
aerobic oxidation of amines to imines, AFP showed remarkable catalytic performance,
with only 0.05 mol% quantity resulting in >85 % high yields at room temperature under
air atmosphere within only one hour reaction. Thus, our study opens up a new avenue
for chemical synthesis of high-performance organic photocatalysts.
13
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Supporting Information
Supporting Information, including some additional figures, is available from the website
or from the authors.
Acknowledgements
Y. M. is grateful for the financial support from the National Natural Science Foundation
of China (21774076 and 51573091), the Program of the Shanghai Committee of
Science and Technology (17JC1403200), the Program of Shanghai Academic Research
Leader (19XD1421700), and the Program of Distinguished Professor of Special
Appointment at Shanghai Institutions of Higher Learning. J.D. and S.K. thank the
Deutsche Forschungsgemeischaft (DFG) for funding (SFB 858). The Instrumental
Analysis Center of Shanghai Jiao Tong University is also acknowledged for some
measurements.
14
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Reference
[1] a) T. Tanaka and A. Osuka, Chem. Soc. Rev., 2015, 44, 943–969; b) J. Yang, M.-
C. Yoon, H. Yoo, P. Kim and D. Kim, Chem. Soc. Rev., 2012, 41, 4808–4826; c)
M. Wolf, A. Herrmann, A. Hirsch and D. M. Guldi, J. Am. Chem. Soc., 2017,
139, 11779–11788; d) W. Zhang, W. Lai and R. Cao, Chem. Rev., 2017, 117,
3717–3797; e) H. Lei, X. Li, J. Meng, W. Zhang and R. Cao, ACS Catal., 2019,
9, 4320–4344.
[2] a) M. Stepien, E. Gonka, M. Zyla and N. Sprutta, Chem. Rev., 2017, 117, 3479–
3716; b) S. Hiroto, Y. Miyake and H. Shinokubo, Chem. Rev., 2017, 117, 2910–
3043; c) Q. Chen, L.Brambilla, L. Daukiya, K. S. Mali, S. D. Feyter, M.
Tommasini, K. Müllen and A. Narita, Angew. Chem. Int. Ed., 2018, 57, 11233–
11237; d) L. Wu, F. Li, Y. Rao, B. Wen, L. Xu, M. Zhou, T. Tanaka, A. Osuka
and J. Song, Angew. Chem. Int. Ed., 2019, 58, 8124–8128.
[3] N. Aratani, D. Kim and A. Osuka, Chem. Asian J., 2009, 4, 1172–1182.
[4] M. H. Sayyad, M. Saleem, K. S. Karimov, M. Yaseen, M. Ali, K. Y. Cheong and
A. F. Mohd Noor, Appl. Phys. A., 2010, 98, 103–109.
[5] a) N. K. Davis, M. Pawlicki and H. L. Anderson, Org. Lett., 2008, 10, 3945 –
3947; b) N. K. Davis, A. L. Thompson and H. L. Anderson, J. Am. Chem. Soc.,
2011, 133, 30–31.
[6] a) S. Richeter, C. Jeandon, J.-P. Gisselbrecht, R. Ruppert, and H. J. Callot, J.
Am. Chem. Soc., 2002, 124, 6168–6179; b) M. Tanaka, S. Hayashi, S. Eu, T.
Umeyama, Y. Matano and H. Imahori, Chem. Commun., 2007, 2069 – 2071; c)
V. V. Diev, K. Hanson, J. D.Zimmerman, S. R. Forrest and M. E. Thompson,
Angew. Chem. Int. Ed., 2010, 49, 5523 – 5526; d) V. V. Diev, C. W. Schlenker,
K. Hanson, Q. Zhong, J. D. Zimmerman, S. R. Forrest and M. E. Thompson, J.
Org. Chem., 2012, 77, 143–159.
[7] N. K. Davis, A. L. Thompson and H. L. Anderson, Org. Lett., 2010,12, 2124–
2127.
[8] T. P. Yoon, M. A. Ischay and J. Du V, Nature Chemistry, 2010, 2, 527-532.
[9] a) J. S. M. Samec, A. H. Ell and J. E. Backvall, Chem. Eur. J., 2005, 11, 2327;
b) S. I. Murahashi, Angew. Chem. Int. Ed., 1995, 34, 2443; c) C. A. Kauffman
and P.L. Caver, Drugs., 1997, 53, 539-549.
15
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
[10] 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 and C. J. Chang, Science, 2015, 349, 1208.
[11] a) A. Prades, E. Peris and M Albrecht, Organometallic., 2011, 30, 1162-1167;
b) E. Zhang, H. Tian, S. Xu, X. Yu and Q. Xu, Org. Lett., 2013, 15, 2704-2707;
c) S. Zhao, C. Liu, Y. Guo, J-C. Xiao and Q-Y. Chen, J. Org. Chem., 2014, 79,
8926-8931; d) K. Marui, A. Nomoto, M. Ueshima and A. Ogawa, Tetrahedron
Lett., 2015, 56, 1200-1202.
[12] a) X. Lang, W. Ma, Y. Zhao, C. Chen, H. Ji, and J. Zhao, J. Chem.-Eur., 2012,
18, 2624-2631; b) S. Zavahir and H. Zhu, Molecules, 2015, 20, 1941-1954; c) S.
Furukawa, Y. Ohno, T. Shishido, K. Teramura and T. Tanaka, ACS Catal., 2011,
1, 1150-1153; d) F. Su, S. C. Mathew, L. Mohlmann, M. Antonietti, X. Wang
and S. Blechert, Angew. Chem., Int. Ed., 2011, 50, 657-660; e) J. Luo, J. Lu and
J. Zhang, J. Mater. Chem. A, 2018, 6,15154-15159; f) M. Wang, L. Li, J. Lu, N.
Luo, X. Zhang and F. Wang, Green Chem., 2017, 19, 5172–5177; g) H. Liu, C.
Xu, D. Li and H-L. Jiang, Angew. Chem. Int. Ed. 2018, 57, 5379 –5383; h) F-J.
Zhao, G. Zhang, Z. Ju, Y-X. Tan and D. Yuan, Inorg. Chem. 2020, 59, 3297-
3303
[13] a) M. Mure and J. P. Klinman, J. Am. Chem. Soc., 1995, 117, 8698-8706; b) A.
E. Wendlandt and S. S. Stahl, Org. Lett., 2012, 14, 2850-2853; -
Kobayashi, J. Am. Chem. Soc., 2012, 134, 13970-
13973.
[14] M. Higuchi, I. Ikeda and T. Hirao, J. Org. Chem., 1997, 62, 1072-1078.
[15] L. Liu, Z. Wang, X. Fu and C-H Yan, Org. Lett., 2012, 14, 5692-5695.
[16] a) X. Lang, H. Ji, C. Chen, W. Ma and J. Zhao, Angew. Chem., Int. Ed., 2011,
123, 4020–4023; b) R. Chen, J-L. Shi, Y. Ma, G. Lin, X. Lang and C. Wang,
Angew. Chem. Int. Ed., 2019, 58, 6430–6434 c) H. Huang, J. Huang and Y-M.
Liu, H-Y. He, Y. Cao and K-N. Fan, Green Chem., 2012, 14, 930-934; d) J. H.
Park, F. Raza, S-J. Jeon, D. B. Yim, H-I. Kim, T. W. Kang and J-H. Kim, J.
Mater. Chem. A., 2016, 4, 14796–14803; e) J. H. Park, K. C. Ko, E. Kim, N.
Park, J. H. Ko, D. H. Ryu, T. K. Ahn, J. Y. Lee and S. U. Son, Org. Lett., 2012,
14, 5502-5505; f) G. Jiang, J. Chen, J. -S. Huang and C. -M. Che, Org. Lett.,
2009, 11, 4568-4571; g) N. Kang, J. H. Park, K. C. Ko, J. Chun, E. Kim, H-W.
16
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Shin, S. M. Lee, H. J. Kim, T. K. Ahn, J. Y. Lee and S. U. Son, Angew. Chem.
Int. Ed., 2013, 52, 6228-6232; h) J. Jin, H-W. Shin, J. H. Park, J. H. Park, E.
Kim, T. K. Ahn, D. H. Ryu and S. U. Son, Organometallic, 2013, 32, 3954-
3959.
[17] a) G. P. Arsenault, E. Bullock, S. F. MacDonald, J. Am. Chem. Soc., 1960, 82,
4348–4386; b) M. Davis, M. O. Senge and O. B. Locos, Z. Naturforsch., 2010,
65b, 1472–1484 c) D. G. Hilmey, M. Abe, M. I. Nelen, C. E. Stilts, G. A. Baker,
S. N. Baker, F. V. Bright, S. R. Davies, S. O. Gollnick, A. R. Oseroff, S. L.
Gibson, R. Hilf and M. R. Detty, Journal of Medicinal Chemistry, 2002, 45,
449-461;
[18] P. J. Chmielewski, L. Latos-G ż ńsk T. Gł w k J. Am. Chem. Soc. 1996,
118, 5690–5701
[19] M. Lan, H. Zhao, H. Yuan, C. Jiang, S. Zuo, Y. Jiang, Dyes and Pigments 2007,
74, 357–362.
[20]W. Wang, Y. Tang, Y. Yu, Chinese Journal of Applied Chemistry, 1989, 6, 54-
56
[21] a) Y. Shiraishi, Y. Sugano, S. Tanaka and T. Hirai, Angew. Chem., Int. Ed.,
2010, 49, 1656-1660; (b)M. Keller, A. S. Sido, P. Pale and J. Sommer, Chem. -
Eur. J., 2009, 15, 2810-2817.
[22] a) A. Gorman, J. Killoran, C. O’ he T. Kenna, W. M. Gallagher and D. F.
O’ hea, J. Am. Chem. Soc., 2004, 126, 10619–10631; b) M. R. Detty and P. B.
Merkel, J. Am. Chem. Soc., 1990, 112, 3845-3855.
17
This article is protected by copyright. All rights reserved.

10.1002/chem.202003398
Chemistry - A European Journal
Entry for the Table of Contents
Article
Pengfei Zhang, Chunyang Yu, Yucheng
Yin, Jörn Droste Sina Klabunde, Michael
Ryan Hansen, and Yiyong Mai*
Bis-Anthracene Fused Porphyrin as An
Efficient Photocatalyst: Facile Synthesis
and Visible-Light-Driven Oxidative
Coupling of Amines
Bis-anthracene fused porphyrin was synthesized in a high yield by a facile protocol.
When serving as a photocatalyst, the new molecule exhibits excellent catalytic
performance for visible-light-induced aerobic oxidation of amines to imines at
ambient condition
18
This article is protected by copyright. All rights reserved.