Positive shift in corrole redox potentials leveraged by modest β-CF3-substitution helps achieve efficient photocatalytic C-H bond functionalization by group 13 complexes

Article abstract of DOI:10.1039/c9dt02150g

Tris- A nd tetrakis-β-trifluoromethylated gallium (3CF₃-Ga, 4CF₃-Ga) and aluminum (3CF₃-Al, 4CF₃-Al) corrole systems were synthesized by a facile "one-pot" approach from the respective tri- A nd tetra-iodo starting compounds using the FSO₂CF₂CO₂Me reagent. The isolated 5,10,15-(tris-pentafluorophenyl)corrole-based compounds set the groundwork for another important β-substituent study in inorganic photocatalysis. As seen previously,-CF₃ group substitution leads to red shifts in both the absorption and emission spectra compared to their unsubstituted counterparts (X. Zhan, et al., Inorg. Chem., 2019, 58, 6184-6198). All CF₃-substituted corrole complexes showed strong fluorescence; 3CF₃-Al possessed the highest fluorescence quantum yield (0.71) among these compounds. The photocatalytic production of bromophenol by way of these photosensitizing complexes was studied demonstrating that tris-trifluoromethylation is an important substitution class, especially when Ga³⁺ is present (experimental TON value in parentheses): 3CF₃-Ga (192) > 4CF₃-Ga (146) > 3CF₃-Al (130) > 4CF₃-Al (56) > 1-Ga (43) > 1-Al (18). The catalytic performance (turn-over number, TON) for benzylbromide formation (from toluene) was found to be: 3CF₃-Ga (225) > 1-Ga (138) > 3CF₃-Al (130) > 4CF₃-Ga (126) > 1-Al (95) > 4CF₃-Al (89); in these trials, benzaldehyde was also detected as a product in which 3CF₃-Ga outperforms the other compounds (TON = 109). The tetra-CF₃-substituted 4CF₃-Ga and 4CF₃-Al species exhibit a dramatic formal positive shift of 116 mV and 126 mV per [CF₃] group, respectively, compared to the unsubstituted parent species 1-Ga and 1-Al. However, the absorbance values (λ_abs = 400 nm) of these corrole complexes (all equally concentrated: 4.0 × 10^-6 M) were 3CF₃-Al (0.23) > 3CF₃-Ga (0.22) > 1-Al (0.21) > 1-Ga (0.20) > 4CF₃-Al (0.19) > 4CF₃-Ga (0.15), which helps rationalize why 3CF₃-Ga performs the best among these catalysts. These new photosensitizers were carefully characterized by ¹H and ¹⁹F NMR spectroscopy to help verify the number and position (symmetry) of the CF₃ groups; 3CF₃-Ga and 3I-Al were structurally characterized. Distortions in the corrole macrocycle imposed by the multiple β-substitution were quantified.

Full text of DOI:10.1039/c9dt02150g

View Article Online
View Journal
Dalton
Transactions
An international journal of inorganic chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Zhan, P. Yadav,
Y. Diskin-Posner, N. Fridman, M. Sundararajan, Z. Ullah, Q. Chen, L. J. Shimon, A. Mahammed, D. G.
Churchill, M. Baik and Z. Gross, Dalton Trans., 2019, DOI: 10.1039/C9DT02150G.
Volume 46
Number 10
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
1
4
March 2017
Pages 3073-3412
Dalton
Transactions
An international journal of inorganic chemistry
rsc.li/dalton
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 0306-0012
COMMUNICATION
Douglas W. Stephen et al.
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
and tellurenyl cations (XH , X = S, Se, Te)
+
rsc.li/dalton

Page 1 of 9
Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
View Article Online
DOI: 10.1039/C9DT02150G
ARTICLE
Positive shift in corrole redox potentials leveraged by modest β‐
CF ‐substitution helps achieve efficient photocatalytic C‐H bond
functionalization for group 13 complexes
3
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
a
c, d
Xuan Zhan , Pinky Yadav , Yael Diskin‐Posner , Natalia Fridman , Mahesh Sundararajan , Zakir
c,d
a
b
a
a,c,d
DOI: 10.1039/x0xx00000x
Ullah , Qiu‐Cheng Chen , Linda J. W. Shimon , Atif Mahammed , David G. Churchill *
Mu‐
*
c, d
a
Hyun Baik
and Zeev Gross *
Tris‐ and tetrakis‐β‐trifluoromethylated gallium (3CF
synthesized by a facile “one‐pot” approach from the respective tri‐ and tetra‐iodo starting compounds using the
FSO CF CO Me reagent (Scheme 1). The isolated 5,10,15‐(tris‐pentafluorophenyl)corrole‐based compounds set the
groundwork for another important β‐substituent study in inorganic photocatalysis. As seen previously, –CF group
substitution leads to red shifts in both the absorption and emission spectra compared to their unsubstituted counterparts
X. Zhan, et al. Inorg. Chem. 2019, 58, 6184‐6198.). All CF ‐ substituted corrole complexes showed strong fluorescence; 3CF
3 3 3 3
‐Ga, 4CF ‐Ga) and aluminum (3CF ‐Al, 4CF ‐Al) corrole systems were
2
2
2
3
(
3
3
‐
Al possessed the highest fluorescence quantum yield (0.71) among these compounds. The photocatalytic production of
bromophenol by way of these photosensitizing complexes was studied demonstrating that tris‐trifluoromethylation is an
important substitution class, especially when Ga3+ is present (experimental TON value in parentheses): 3CF
‐Ga (192) ＞
‐Al (56) ＞ 1‐Ga (43) ＞ 1‐Al (18). The catalytic performance (turn‐over number, TON)
for benzylbromide formation (from toluene) was found to be: 3CF ‐Ga (225) ＞ 1‐Ga (138) ＞ 3CF ‐Al (130) ＞ 4CF ‐Ga (126)
1‐Al (95) ＞ 4CF ‐Al (89); in these trials, benzaldehyde was also detected as a product in which 3CF ‐Ga outperforms the
other compounds (TON = 109). The tetra‐CF ‐substituted 4CF ‐Ga and 4CF ‐Al species exhibit a dramatic formal positive
shift of 116 mV and 126 mV per [CF ] group, respectively, compared to the unsubstituted parent species 1‐Ga and 1‐Al.
However, the absorbance values (λabs = 400 nm) of these corrole complexes (all equally concentrated: 4.0 × 10‐6 M) were
3
4CF
3
‐Ga (146) ＞ 3CF
3
‐Al (130) ＞ 4CF
3
3
3
3
＞
3
3
3
3
3
3
3
CF
why 3CF
19F NMR spectroscopy to help verify the number and position (symmetry) of the CF
3
‐Al (0.23)＞3CF
3
‐Ga (0.22)＞1‐Al (0.21)＞1‐Ga (0.20)＞4CF
3
‐Al (0.19)＞4CF
3
‐Ga (0.15) (Fig 5 (a)), which helps rationalize
1
3
‐Ga performs the best among these catalysts. These new photosensitizers were carefully characterized by H and
3
groups; 3CF ‐Ga and 3I‐Al were
3
structurally characterized. Distortions in the corrole macrocycle imposed by the multiple β‐substitution were quantified.
Introduction
Photosensitization in small molecules almost always requires a π‐
delocalized chromophoric system; its catalytic activity corresponds
with the light energy provided, as well as conditions and the solvent
a.
X. Zhan, Dr. P. Yadav, Dr. N. Fridman, Q‐C. Chen, Dr. A. Mahammed, Prof. Dr. D.
G. Churchill, Prof. Dr. Z. Gross
environment, etc. Since the tuning of the aromatic π‐system is best
when it is rigid, effectively planar, structurally sound (robust)
bioinspired, as well as easily functionalized, porphyrinoid systems of
various types continue to be employed and interrogated as much as
ever.1 Recent photocatalysis articles dealing with C‐H bond
functionalization include studies in which C‐H bonds can be oxidized
Schulich Faculty of Chemistry
Technion‐Israel Institute of Technology
Haifa 32000 (Israel)
E‐mail: ch10zg@techunix.technion.ac.il.
Dr. Y. Diskin‐Posner, Dr. L. J. W. Shimon
Department of Chemical Research Support
Weizmann Institute of Science
Rehovot 76100 (Israel).
Dr M. Sundararajan, Dr Z. Ullah, prof. M.‐H. Baik and Prof. Dr. D. G. Churchill
b.
c.
1
and halogenated, etc.
Department of Chemistry
Korea Advanced Institute of Science and Technology (KAIST)
Daejeon (Republic of Korea)
In chromophores as well as medicinal compounds, fluorine
substituent chemistry continues to develop very rapidly.2 An
E‐mail: david.churchill.korea@gmail.com
d.
estimated 30% of modern molecular pharmaceuticals contain at
least one fluorine atom; this substitution enhances lipophilicity and
Dr M. Sundararajan, Dr Z. Ullah, prof. M.‐H. Baik and Prof. Dr. D. G. Churchill
Center for Catalytic Hydrocarbon Functionalizations
Institute for Basic Science (IBS)
3
membrane permeability. Therefore, with sterics roughly of an H‐
Daejeon (Republic of Korea)
E‐mail: david.churchill.korea@gmail.com
atom, but with great polarization capacity, the tweaking of the
electronics and other molecular properties has, in many cases, been
†
Dedicated to O. T. Beachley Jr. (1937‐2018) a longtime faculty member at the
University at Buffalo and specialist in main group chemistry.
realized. –CF
values (σ
groups possess extraordinary Hammett parameter
3
Electronic Supplementary Information (ESI) available: details of all the experimental
data and all spectra of characterization. See DOI: 10.1039/x0xx00000x
4
m
= 0.43; σ
p
= 0.54). The F group is stable, chemically
Please do not adjust margins

Pleas
D
e
a
d
lt
o
o nn o
T
t
ra
a
n
d
s
j
a
u
c
s
t
t
io
m
n
a
s
rgins
Page 2 of 9
View Article Online
DOI: 10.1039/C9DT02150G
ARTICLE
Journal Name
5
compatible, and biocompatible. Incorporation of such chemical Scheme. 1 The synthetic route of target compounds: 3CF
3 3
‐Ga, 3CF ‐
groups in the form of trifluoromethylation is also straight‐forward Al, 4CF ‐Ga and 4CF ‐Al. All axial ligands of these compounds have
3
3
and paves the way for the preparation of natural or synthetic been omitted for clarity. Synthetic methods i and ii have been
6
(
medicinal) fluoroorganic/ fluoroorganometallic derivatives. While reported previously and their procedures can be found in the
1
4
there have been a variety of synthetic approaches to corrole β‐ published literature. (i) An excess stoichiometric amount of NIS (N‐
position substitution chemistry, those bearing both bare fluorines, as iodosuccinimide) was added in acetonitrile at room temperature for
well as CF
3
groups, prove especially intriguing in the context of 1 h to give 4I‐Ga / 4I‐Al; (ii) Treatment with excess I
2
and pyridine and
photosensitizer design. Recent publication have addressed the utility refluxing in toluene for
1 h gives 3I‐Ga / 3I‐Al; (iii)
7
of ‐CF
3
‐containing corroles which, as with the original synthetic issue FSO
2
CF
2
CO
2
Me/CuI, DMF, 100℃, 10 h.
6 5
that lead to the widespread use of the meso ‐C F substituents, also
revolves around achieving practical synthetic methodology.
Structure‐function relationships in the context of photocatalysis can
be elucidated from the corrole systems’s reliable functional group
Scheme 1 depicts the synthetic method for the preparation of the
target compounds under discussion. The synthesis of precursors (3I‐
1
4
7
Ga, 4I‐Ga, 3I‐Al, 4I‐Al) have been described previously. The
layout and its tunable and optimizable properties.
treatment of the appropriately iodinated metallocorroles with
methyl–2,2–difluoro–2–(fluorosulfonyl)acetate
2 2 2
(FSO CF CO Me)
Perfluoroalkyl‐substituted corroles and their metallic complexes and CuI in DMF at 100 °C under argon atmosphere yielded colored β‐
have shown their robust potential in energy‐related catalysis, organic CF
catalysis, and medicinal chemistry utility. In 2008, Ghosh and were logically exchanged for ‐CF
3
‐substituted target compounds in 42‐53% yield. All iodo positions
groups, as expected. All new
8
3
coworkers reported on the copper β‐octakis(trifluoromethyl) metallocorroles were characterized by various spectroscopic
corroles, and later, on the meso‐CF
and its cobalt complex. Recently, we reported the halogenation on Figs. S1‐S8), MS (see Figs. S9‐S14) and UV‐vis. Through the NMR
3
substituted free‐base corrole techniques viz., NMR spectroscopy (complete versions of spectra see
9
the β‐position of 5,10,15‐(tris‐pentafluorophenyl)corrole (tpfc) spectroscopic studies, 3CF
which helped tune the redox and photophysical properties.
3
‐Ga and 3CF
singlets at 9.43 and 9.27 ppm, respectively; whereas two doublets of
Recently, our group fruitfully achieved the synthesis of meso‐ 4CF ‐Ga (8.30 ppm and 8.13 ppm) and 4CF ‐Al (8.10 ppm and 7.91
,10,15‐tris‐trifluoromethylated corrole (TFC) and its metal ppm) corresponding to β‐pyrrole protons were found up‐field
3
‐Al were found to exhibit
1
0
3
3
5
1
1
complexes. In the meantime, we successfully prepared the partially shifted. The greater number of CF
3
‐substitutents results in higher
β–CF substituted gold corroles; a dramatic effect of CF ‐substitution symmetry of the macrocycle and fewer signals, and signals which are
3
3
is imparted to the photophysical and redox properties of the again drawn upfield (Fig. 1a). Spectroscopic characterization was
system.12 Therefore, papers dealing with CF
group corroles, while extended to F NMR spectroscopy confirmed the assignments of the
19
3
1
still rare, are already starting to redefine the photocatalytic research symmetric tetrasubstituted species made by H NMR: three para‐F
front.7 Unlike the gold corrole, which was non‐fluorescent, and resonance signals showed 1:2 integration ratio rather than a 2:1 or
different in many ways from P chemistry, we can adapt intriguing 1:1:1 ratio (observed in 3CF
photophysical features observed in examples of corroles featuring spectroscopic results matched the number of groups and extent of
main group elements as the central atom; therefore, β‐CF molecular symmetry exhibited and reflects the expected for the
3 3
‐Al and 3CF ‐Ga) (Fig. 1b). These
3
substitution could help turn on C‐H bond activation chemistry when molecular structures.
considering the β–unsubstituted aluminium (1‐Al) and gallium (1‐Ga)
species. Thus, we set out to prepare partially β‐trifluoromethylated
aluminium and gallium complexes to obtain deeper insights into the
3
effect of CF ‐substitution on photophysical and electrochemical
redox properties. With the issue of C‐H bond activation at hand,
Gryko and co‐workers reported that porphyrins can be used as
photocatalysts in, e.g., C‐C bond formation reactions and C‐E
1
3
activation reactions; this aroused great interest to investigate
whether examples of corrole complexes can be found that signify
promising precursors/candidates for photo‐synthesis applications.
Thus, the potential of these newly synthesized non‐precious element
containing corroles was addressed using light energy; readily
available HBr is employed to achieve an understanding of the
patterns of organic substrate functionalization.
Results and discussion
1
Fig. 1 (a) H NMR spectra (CDCl
pyrrole CH’s for 3CF ‐Ga, 3CF ‐Al and 4CF
recorded in C ; (b) their corresponding partial F NMR spectra
CDCl , 377 MHz), focusing on para‐F [–C ] atoms only.
3
, 400 MHz) of the available β‐
3
3
3
‐Ga, 4CF ‐Al were
3
1
9
C
6 5
F
C
6
F
5
C
6
F
5
6 6
D
(
3
6 5
F
N
N
N
N
N
N
N
N
iii
This work
N
N
N
N
i or ii
C
6
F
5
M
C
6
F
5
C
6
F
5
M
C
X
6 5
F
C
6
F
5
M
C
6 5
F
X
X
X
Y
X
Y
X
3
Experimental conditions were found for compounds 3CF ‐Ga
1
-Ga: M = Ga
3CF
4CF
3CF
-Ga: X = CF
-Ga: X = Y= CF
-Al: X = CF
, Y = H, M = Al, 36 %
4CF -Al: X = Y= CF
, M = Al, 42 %
, Y = H, M = Ga, 53 %
3
I-Ga: X = I, Y = H, M = Ga
4I-Ga: X = Y= I, M = Ga
I-Al: X = I, Y = H, M = Al
I-Al: X = Y= I, M = Al
3
3
1-Al: M = Al
3
3
, M = Ga, 48 %
and 3I‐Al to enable them to crystallize out of solution reasonably
well. X‐ray quality crystals of 3CF ‐Ga were therefore obtained by
3
3
3
4
3
3
3
slow evaporation from ethanol/hexane solution. X‐ray quality
2
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 9
Dalt Transactions
Please d oo nn ot adjust margins
View Article Online
DOI: 10.1039/C9DT02150G
Journal Name
ARTICLE
crystals of 3I‐Al were obtained by slow evaporation of congested CF
chloroform/hexane solution with an addition of a few drops of 3CF ‐Al and 4CF
pyridine to provide the central metal sites access to a coordinating and 4CF ‐Ga species. –CF
solvent species. The structure of 3CF ‐Ga was confirmed by X‐ray terms of the emission peak ranging from an increase in 12‐17 nm as
crystallography. Interestingly, in this complex, we found the gallium observed from the formal addition of a ‐CF group onto 3CF ‐Ga/Al
3
groups located at the 2, 3, 17 and 18 positions. The
3
3
‐Al showed stronger fluorescence than the 3CF
3
‐Ga
3
3
substitution also created the red shift in
3
3
3
metal centre was not only coordinated to the N‐atoms from four to give 4CF
pyrrole units but also bound to a solvent molecule that refined well
as a water molecule; the single axial ligand assigned structurally as a
3
‐Ga/Al (see Table. S2).
[H
2
O] unit allowed the metal complex to adopt a domed
conformation (Fig. 2); the Ga‐O bond length was observed to be
.870(4) Å. As expected from the electronic effect of the β‐
1
substituted iodine, the average Al‐Npyrrole bond length of 3I‐Al was
found to be 1.899(5) Å which was slightly longer than the bond length
found for 1‐Al (1.892(5) Å); whereas the average Al‐Npyridine bond
length of 3I‐Al (2.154(4) Å) was found to be somewhat shorter than
that found in 1‐Al (2.183(8) Å). All selected structural data was shown
in Table. S1; Interestingly, the 3CF
3
‐Ga species exhibited a more
distorted macrocycle compared to the previous reported iodinated
1
]
species 3I‐Ga : the deviation of the central gallium from the [N
corrole plane (0.0232(6) Å) is somewhat greater than that found for
I‐Ga (0.0182(4)Å). The dihedral “saddling” angles also
demonstrated this notion: the sum values of four dihedral angles
were determined as 34.80° (3I‐Ga) vs 36.67° (3CF ‐Ga).
4
]
3
Fig.3 (a) The UV‐vis spectra of the investigated compounds: 3CF ‐
‐
5
‐5
‐5
Ga (1.55 x 10 M), 3CF
3
‐Al (1.34 x 10 M), 4CF
3
‐Ga (1.65 x 10 M),
3
‐Al (2.65 x 10‐ M). (b) The fluorescence emission spectra of
5
4CF
3
studied compounds under the same absorbance (0.05 OD) with the
Soret band of TPP also (5,10,15,20‐tetraphenylporphyrin) recorded
for comparison. All data recorded in toluene under room
temperature and aerobic conditions were and the excitation
wavelength was set at 420 nm.
3
3
To study the influence of CF ‐substitution on redox potentials of
gallium and aluminium corroles, the cyclic voltammetry (CV)
experiments were obtained and the data was analysed (See Fig. 4,
Fig. S15 and Table. S3).
Fig. 2. Side views of the X‐ray crystal structures of 3I‐Al (a) and
CF ‐Ga (b); (c) A comparison of the dihedral angles (°) and sum
values found for 3I‐Ga and 3CF ‐Ga.
3
3
3
We undertook a full UV‐vis and fluorescence studies of the corrole
photosensitizer molecules as well. The UV‐vis absorption (see Fig. 3a)
Fig. 4 (a) CV traces of 1‐Ga, 3CF
voltammogram region of compound oxidation. (b) CV traces of 1‐Al,
CF ‐Al and 4CF ‐Al in the voltammogram region of compound
oxidation. Glassy carbon working electrode, and an Ag/AgNO ref.
CN with TBAP. Scan rate of 100 mV s were
3 3
‐Ga and 4CF ‐Ga in the
spectral data of β–CF
electron‐withdrawing nature of the –CF
strength of the spectral absorption to the red region. Tetra–CF
3
substituted corroles are listed in Table. S2. The
3
3
3
3
group attenuated the
3
‐
‐1
3
electrode. Solvent: CH
applied.
3
substituted aluminium and gallium corroles displayed a small 5‐6 nm
shift in the Soret band maxima (centered around 420 nm); a more
significant 19‐27 nm shift was observed for the Q‐band maxima,
compared to the non‐substituted 1‐Al and 1‐Ga species. All CF
substituted corrole complexes showed strong fluorescence; 3CF
‐Al incorporation as well as assess HOMO‐LUMO levels. Several
possessed the highest fluorescence quantum yield (Φ
= 0.71) among interesting points are noted here: (i) 4CF ‐Ga and 4CF ‐Al exhibited
these compounds. Interestingly, 4CF ‐Ga showed
longer two reduction processes at ‐1.07 and ‐1.64 V; ‐1.11 and ‐1.59 V,
fluorescence lifetime (4.54 ns) than that for 1‐Ga (2.21 ns) and respectively (see Fig. S15 and Table. S3). (ii) Generally, with the same
3
‐
CV studies help elucidate the electronic effects of substituent
3
F
3
3
3
a
8
‐1
exhibited the largest non‐radiative rate constant (Knr = 4.02 × 10 s ) β‐functionalization, the Ga corrole shows a more positive shift in
3
+
(
see Table. S1) which can be explained by the “heavy atom effect” redox potentials compared to the Al corrole; however, notably, the
st
emanating from the gallium center, as well as by the effect of
1
reduction potential for 3CF
3
‐Al (‐1.24 V) experienced a more
distortion from planarity based on the presence of the sterically positive shift than that for 3CF
3
‐Ga (‐1.26 V). (iii) The oxidation
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 3
Please do not adjust margins

Pleas
D
e
a
d
lt
o
o nn o
T
t
ra
a
n
d
s
j
a
u
c
s
t
t
io
m
n
a
s
rgins
Page 4 of 9
View Article Online
DOI: 10.1039/C9DT02150G
ARTICLE
Journal Name
OH
CH
OH
CH
OH
3
potential values observed for CF ‐substituted Ga/Al corroles is found
Br
HBr/ Air
to be below 1.0 V; 4CF
oxidation potential located at 0.83 V. 4CF
potential towards a more positive range by 116‐126 mV per –CF
group compared to their unsubstituted counterparts (1‐Ga/1‐Al).
The effect of the CF group on redox potentials is more prominent
than halogen substitution; Cl‐substitution, for example, illustrates a
3
‐Ga showed the most positive shift in
(1)
+
Cat/LED
(400 nm)
3
‐Ga/Al shifts the oxidation
Br
3
3
2
Br
CHO
HBr/ Air
Cat/LED
3
(2)
+
(
400 nm)
1
4
formal maximum shift of 58 mV per group on the system. Moving
from 3CF
3
to 4CF
3
‐substitution, a greater positive shift in redox
st
potentials was observed; 113 mV on the 1 oxidation potential and
Scheme. 2 Schemes for the photo‐catalytic bromination of phenol
st
1
87 mV shift on the 1 reduction potential for the same metal center and toluene under discussion here.
shows the profound effect of the formal incorporation of a single
extra ‐CF
3
CF to 4CF (2.02 V to 1.90 V for gallium complexes and from 1.87 V
3
group. iv). The HOMO‐LUMO energy gap decreased from Table. 1 Results from metallocorrole‐catalyzed bromination of
phenol giving both ortho‐brominated and para‐brominated phenol.
3
3
to 1.85 V for aluminium complexes). These findings remind us that
trifluoromethylation is a good synthetic approach to help shift the
redox potentials positive, and thus in lowering the HOMO‐LUMO
energy gap.
Entry
Catalyst
Irradiation
time (h)
λ of lamp (nm) Bromo‐Phenol
a
(TON)
The dramatic positive shift in redox potentials of these newly
CF ‐ substituted gallium and aluminium corrole complexes,
3
combined with their nature of photosensitization, inspired us to
explore and develop their photocatalytic potential. The facile
bromination of organic substrates is a research topic of significant
interest due to its versatile (and potential emergent) applications in
industrial and medicinal use; brominated (halogenated) organic
compounds, especially aromatics, are versatile precursors for
carbon−carbon and carbon−heteroatom bond formaꢀon such as the
famous named cross‐coupling reactions (i.e., the illustrious Suzuki,
Heck, Stille coupling reactions). Specifically, we used phenol as a
substrate and HBr as the bromide source along with the
photosensitizer corrole photocatalyst taken under irradiation by a
LED lamp (λexcit = 395 ‐ 405 nm, 200 W); different gallium and
aluminium corroles were explored as catalysts to investigate the
structure‐function relationship of the catalysis (see additional
operating information in the Supporting Information). The reaction
affords two mono‐brominated phenol compounds (ortho‐ and para‐
1
2
3
4
5
6
7
8
1‐Ga
1‐Al
3
3
3
3
3
3
3
3
400
400
400
595
400
400
400
400
43
18
192
30
130
146
59
‐
3CF
3CF
3CF
4CF
4CF
No
3
3
3
3
3
‐Ga
‐Ga
‐Al
1
5
,
see Scheme 2 (1)). All samples studied remained stable during the
‐Ga
‐Al
photocatalytic process as exemplified by a close comparison of the
3
spectra e.g. for 3CF ‐Ga (Fig. 5b) acquired before and after
photocatalysis.
catalyst
9
3CF
3CF
3
3
‐Ga
‐Ga
3
Dark
400
‐
‐
10
12
(
anaerobic)
Fig. 5 (a) UV‐vis spectra of investigated compounds under the
‐
6
same concentration of 4 × 10 M; inset: the table of the absorbance
a
Turnover number of both ortho‐ and para‐mono‐brominated
phenol formed as detected by GC (see Supporting Information).
3
values at 400 nm; (b) UV‐vis spectra of reaction mixture of 3CF ‐Ga
with HBr before and after 24 h of irradiation.
The corresponding results have been included and summarized in
Table. 1. Photocatalytic results obtained under the same conditions
4
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 9
Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
View Article Online
DOI: 10.1039/C9DT02150G
Journal Name
ARTICLE
‐
afforded turn over number values (TON) of 43, 18, 192, 130, 146 Br to form Br‐Br which is then able to undergo reaction with the
and 56 for compounds 1‐Ga, 1‐Al, 3CF
CF ‐Al, respectively, when they were used as catalysts. The
photocatalytic performance for photo‐synthesis of bromophenol of
these complexes is 3CF ‐Ga＞4CF ‐Ga＞3CF ‐Al＞4CF ‐Al＞1‐Ga
1‐Al, which is roughly in the order of the 1 oxidation potential
values of these complexes: 4CF ‐Ga (0.83 V)＞3CF ‐Ga (0.77 V)＞
CF ‐Al (0.74 V)＞3CF ‐Al (0.62 V)＞1‐Ga (0.37 V)＞1‐Al (0.23 V),
3 3 3
‐Ga, 3CF ‐Al, 4CF ‐Ga and organic C(Ar)‐H group.
4
3
3
3
3
3
st
＞
Entry
Catalyst
Irradiation
time (h)
λ of Benzyl
lamp bromide (TON)b
nm) (TON)a
Benzaldehyde
3
3
4
3
3
(
which confirmed that the complexes which possessed more
positive redox potentials tended to have greater efficiency of
photooxidation. The emitting light source here is the LED
possessing a wavelength of ca. 400 nm; thus, under the same
concentrations, the complexes which had stronger absorbance at
1
2
3
4
5
6
7
8
9
1‐Ga
1‐Al
5
400
400
400
595
400
400
400
400
Dark
400
138
95
225
24
130
126
89
‐
46
42
109
‐
1
6
4
00 nm should perform more efficiently in photocatalysis. The
absorbance at the wavelength of 400 nm of these corrole
5
complexes at exactly the same concentration (4 × 10 ‐ mol L ) was
measured and found to be in the order of 3CF ‐Al (0.23)＞3CF ‐Ga
‐Al (0.19)＞4CF ‐Ga (0.15)
Fig. 5 (a)); the values help rationalize why 3CF ‐Ga performed the
6
‐1
3
3
(
(
0.22)＞1‐Al (0.21)＞1‐Ga (0.20)＞4CF
3
3
3CF
3CF
3CF
3
3
3
‐Ga
‐Ga
‐Al
5
3
best among these catalysts in the present study.
5
Halogenations of alkyl aromatics are very important and
1
7
2
versatile reactions. After successful trials of bromination of sp ‐C
(
phenol) herein, we further introduced this novel method of the
5
49
50
30
‐
3
photo‐bromination of toluene (sp ‐C) for converting it to benzyl
bromide (Scheme 2, entry 2). All new prepared aluminium and
gallium corroles were investigated as the photocatalysts in driving
this conversion. After irradiation for 5 hours under the LED
4CF ‐Ga
3
5
(
experimental details are provided in the Supporting Information),
the TON data was acquired; the results obtained by these
4CF
3
‐Al
5
metallocorroles have been included in Table. 2. The catalytic
performance (TON) for these catalysts was found to be: 3CF
225) ＞1‐Ga (138) ＞3CF ‐Al (130) ＞4CF ‐Ga (126) ＞1‐Al (95) ＞
CF ‐Al (89). Besides benzyl bromide, benzaldehyde formation was
also detected, determined to be a side‐product involving smaller
turnover efficiency. 3CF ‐Ga outperforms others for the toluene‐to‐
3
‐Ga
(
3
3
No catalyst
5
4
3
3
3CF
3CF
3
3
‐Ga
‐Ga
5
‐
‐
benzaldehyde conversion among these catalysts, with a TON of 109
for benzaldehyde and TON of 225 for benzyl bromide. The
outstanding performance of 3CF ‐Ga helped confirm and support
3
our above explanation based on both absorbance and CV data.
Considering the Q band absorption around 600 nm of studied
corrole complexes, we wondered the catalytic performance using
the LED with irradiation wavelength at the Q band absorption; we
adopted one LED (λexcit = 595 nm, 200 W) as the irradiation source
1
0
24
‐
‐
(anaerobic)
Table. 2 Metallocorrole‐catalyzed bromination of toluene giving
both products of benzyl bromide and benzaldehyde.
3
and take the best catalyst‐3CF ‐Ga as an example, conducted the
phenol and toluene assays under the same concentration and
irradiation time as before. The results were shown in Table 1 (entry
a
Turnover number of benzyl bromide as detected by GC (See
4) and Table 2 (entry 4); the turnover number (TON) of the photo‐
b
Supporting Information); Turnover number of benzaldehyde
detected by GC.
bromination of phenol and toluene were determined of 30 and 24,
respectively, which suggesting the much worse catalytic efficiency
compared to assays using the LED (λexcit = 395 ‐ 405 nm, 200 W). The
observed reduced product yields under red light irradiation (λexcit
=
The mechanism of conversion from bromide to bromine in the
context of corrole research has been detailed by our previous
5
95 nm, 200 W) using the most active photocatalysts herein was not
surprising; the absence of benzaldehyde as a product suggests that
the oxygen‐involved catalytic reaction system was poorly triggered
under red light irradiation. Benzaldehyde may form, but in amounts
too miniscule to be detected by GC. Detailing the accessibility of the
different possible photolytic pathways under different light sources
will be an important objective in future studies. Clearly, under red
light irradiation the major reaction is still at play: photooxidation of
7
,16
work. Additionally, the photocatalytic bromination mechanism of
aromatics, as well as related oxygenation reactions have been
investigated thoroughly by S. Fukuzumi and coworkers.18 These
authors suggested that the aromatic molecule would take the form
‐
of a radical cation and undergo reaction with Br to produce the
∙
radical adduct which would then be dehydrogenated by HO
2
to
generate brominated products; on the other hand, the radical cation
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 5
Please do not adjust margins

Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
Page 6 of 9
View Article Online
DOI: 10.1039/C9DT02150G
ARTICLE
Journal Name
would undergo deprotonation and be followed by fast oxygen redox properties and can contribute to differences in
addition and finally disproportionation to form the corresponding
photocatalysis. Therefore, their photophysical and redox
properties of 3CF ‐Al 4CF ‐Al 3CF ‐Ga 4CF ‐Ga were clearly
aldehyde. The formation of H
2
O
2
here serves as support for the
3
,
3
,
3
,
3
‐
‐
superoxide anion mechanism; H
2
O
2
was detected indeed, via I / I
3
delineated. Our work is helpful for researchers seeking future
designs of corroles: those wanting to (i) develop new classes of
non‐precious metal containing photocatalysts/photosensitizers
and (ii) those seeking to unlock inherent photocatalysis in
uninitiated systems.
1
9
method monitored by UV in one reaction mixture (when using
CF ‐Ga as a catalyst for the bromination of phenol) after irradiation
Supporting Information). After adding excess TBAI
tetrabutylammonium iodide), the UV‐vis spectrum showed typical
3
3
(
(
‐
3
absorption peaks of I in acetonitrile (Fig. S16).
Experimental
Conclusions
3
We have successfully prepared tris‐ and tetra‐ β‐CF ‐substituted
gallium and aluminium tpfc from the corresponding iodo‐ See the Supporting Information for further full experimental details.
containing precursors. These novel products were prepared in
sufficient yield in “one pot”; compound purity via excellent
chromatographic separation allowed for the study of important
substituent effects in photocatalytic studies. For a first measure,
Synthesis of 3CF
0.19 g, 1 mmol) were dissolved in 5‐10 mL DMF within 5 min under
argon. Then, methyl–2,2–difluoro–2–(fluorosulfonyl) acetate
FSO CF CO Me) (0.13 mL, 1 mmol) was added into the reaction and
the reaction flask was maintained at a temperature of 100 ℃. After
an ample time of 10 h, the reaction was monitored by TLC. After all
3
‐Ga. Dry portions of 3I‐Ga (40 mg, 32 μmol) and CuI
(
–
CF
emission spectra compared to their unsubstituted
counterparts. By way of CV, the tetra‐CF ‐substituted 4CF ‐Ga
and 4CF
mV, respectively, per ‐CF
completely β‐unsubstituted parent species 1‐Ga and 1‐Al
3
group substitution leads to red shifts in the absorption and
(
2
2
2
3
3
3
‐Al exhibit a dramatic positive shift of 116 mV and 126 starting materials were consumed, the reaction was stopped and the
3
group present when compared to the components were separated between water and CH
2 2
Cl (1: 1 by
.
volume) fractions; the organic phase was then evaporated. The
greenish crude product was purified using silica gel chromatography
with ethyl acetate and hexane (1:1 by volume) as the mobile phase.
The fluorescent fraction was clear by inspection and
collected/isolated; the involatile product was recrystallized using
While the NMR spectroscopic characterization of the four
compounds helps generate a nice comparison graphically due
to the obtained spectra, the trisubstituted version with gallium,
with three groups instead of four, was found to be the top
performer! The absorbance of these corrole complexes under
the same concentration of 4 × 10 ‐6 mol L were determined to
CH
2
Cl
2
and hexane (1:1 by volume), to obtain a pure green solid
1
portion of 3CF
MHz, CDCl
3
‐Ga obtained in a yield of 53 % (17 mg). H NMR (400
‐1
3
): δ = 9.43 (s, 1H), 8.59 (overlapping d, 2H), 8.42
be in the order of 3CF
1‐Ga (0.20) 4CF ‐Al (0.19)
served to help rationalize why the aforementioned 3CF
3
‐‐Al (0.23)
＞
3
3CF ‐Ga (0.22)＞1‐Al (0.21)
(
(
overlapping d, 2H), 7.34 (t, JH‐H = 7.56 Hz, 2H, pyridine‐H), 6.78
＞
＞
3
＞4CF
3
‐Ga (0.15) (Fig 5a), which
19
broad s, 4H, pyridine‐H), 6.14 (broad s, 4H, pyridine‐H). F NMR
3
‐Ga (377 MHz, CDCl ): δ = ‐48.88 (q, J = 12.05 Hz, 3F), ‐50.52 (q, JF‐F
3 F‐F
=
performed the best among these catalysts under the given 11.98 Hz, 3F), ‐53.25 (s, 3F), ‐137.65 (q, JF‐F = 9.30 Hz, 4F, ortho‐F), ‐
conditions. Importantly, more than a 100 mV positive shift per 138.03 (m, 2F, ortho‐F), ‐151.85 (q, JF‐F = 22.65 Hz, 2F, para‐F), ‐
1
52.08 (t, JF‐F = 21.90 Hz, para‐F), ‐161.19 (m, 2F, meta‐F), ‐162.85
–
3
CF was determined, compared to the fully unsubstituted
‐
(m, 4F, meta‐F). MS (APCI, negative mode) for C40
H
5
F
24
4
N Ga: m/z =
species 1‐Ga and 1‐Al. This trifluoromethylation approach
rendered the corrole complexes more efficient as
photocatalysts in driving the photobromination of aromatic
compounds here, as exemplified by phenol and toluene as
starting materials. The general findings for the photocatalysis
1065.9381 (calculated), 1065.9297 (observed).
Synthesis of 4CF
0.23 g, 1.2 mmol) were dissolved in 5‐10 mL DMF after 5 min under
argon. Then, methyl–2,2–difluoro–2–(fluorosulfonyl) acetate
Ga (TON = 192) was much more active over the non‐ (FSO CF CO Me) (0.16 mL, 1.2 mmol) was added into the reaction
3
‐Ga. A dry portion of 4I‐Ga (40 mg, 30 μmol) and CuI
(
3
are from phenol to 2‐ or 4‐bromophenol; the compound 3CF ‐
2
2
2
functionalized species 1‐Ga and 1‐Al. For benzyl bromide, 3CF
3
‐
solution and the temperature was maintained at 100 ℃. The reaction
was monitored by TLC. After an ample time of 10 h, the reaction was
Ga (TON = 225) dominated. Benzaldehyde was also detected
with a relatively smaller turnover efficiency; it is a side product
due to a separate reaction. Also, it is found to be highest when
stopped, and the components were separated with water and CH
2 2
Cl
(
1:1 by volume); then the organic phase was evaporated. The crude
product, which was green, was then purified using silica gel
chromatography in which ethyl acetate and hexane (1:3 by volume)
served as the mobile phase. The fluorescent fraction was clear with
3
3
CF ‐Ga is used. These photosensitizing compounds were
1
19
isolated and carefully characterized by H and F NMR
spectroscopy to determine the number and positioning of the
the naked eye and isolated; the product was recrystallized by CH
and hexane (1:1 by volume) to give a pure green solid portion of 4CF
of shifting of the signals, but also the degree of symmetry that Ga obtained in the yield of 48 % (15 mg).
H NMR (400 MHz, CDCl3):
the signals are revealing. Characterization also involved single‐ δ = 8.30 (d, JH‐H = 4.90 Hz, 2H), 8.13 (d, JH‐H = 4.93 Hz, 2H), 7.44 (t, JH‐
crystal characterization for 3CF ‐Ga The multiple
= 7.53 Hz, 2H, pyridine‐H), 6.91 (broad s, 4H, pyridine‐H), 6.53
trifluoromethylation groups induce distortions on the corrole (broad s, 4H, pyridine‐H)). F NMR (377 MHz, C
2 2
Cl
3
CF groups which involved, interpreting not only of the extent
3
‐
1
3
.
H
1
9
6
D
6
): δ = ‐49.21 (s, 6F),
‐49.31 (s, 6F), ‐138.78 (m, 6F, ortho‐F), ‐150.37 (t, JF‐F = 22.93 Hz, 1F,
macrocycle as judged by X‐ray structural comparisons. As seen
in previous studies, these deformations induced differences in
para‐F), ‐150.49 (t, JF‐F = 22.57 Hz, 2F, para‐F), ‐160.87 (m, 2F, meta‐
6
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 9
Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
View Article Online
DOI: 10.1039/C9DT02150G
Journal Name
F), ‐162.66 (m, 4F, meta‐F). MS‐ (APCI, negative mode) for Crystal Data for 3CF
ARTICLE
3
‐Ga: moiety formula: C40
7 4 5
H F24GaN O,2(C
24GaN O, M = 1243.42; monoclinic, space
C
41
H
4
F
27
N
4
Ga: m/z = 1133.9255 (calculated), 1133.9182 (observed). N); formula: C50
H
5
H
17
F
6
group P2 /c (14), a = 24.567(7) Å, b = 7.523(2) Å, c = 25.895(7) Å, V =
1
3
3
‐1
4
695.3 Å , Z = 4, T = 200 K, D
completeness = 0.957, θ(max) = 25.053, R (reflections) = 0.0754
5775), wR (reflections) = 0.2048 (7951), S = 0.893, Npar = 728, CCDC
c
= 1.75746 g/cm , µ (mm ) = 0.730, Data
Synthesis of 3CF
0.19 g, 1.0 mmol) was dissolved in 5‐10 mL DMF after the solution
was sparged for 5 min under the argon atmosphere Then, methyl–
,2–difluoro–2–(fluorosulfonyl) acetate (FSO CF CO Me) was added
0.13 mL, 1.0 mmol) into the reaction with the reaction being
3
‐Al. A dry portion of 3I‐Al (40 mg, 33 μmol) and CuI
(
(
2
code: CCDC1915746.
2
(
2
2
2
maintained at 100 ℃. The reaction was monitored by TLC, after an
ample time of 10 h, the reaction mixture was quenched and
separated with water and CH Cl (1:1 by volume); then, the solution
2 2
Conflicts of interest
containing the organic phase was purified by doing a silica gel
chromatography in which ethyl acetate and hexane (1: 1 by volume)
constituted the mobile phase. The fluorescent band was clearly
identified by inspection and isolated; the non‐volatile product was
There are no conflicts to declare.
Acknowledgements
Z. G. acknowledges the support of this research by a grant from
recrystallized using CH
2 2
Cl and hexane (1: 1) to afford a pure green
1
solid portion of 3CF ‐Al obtained in a yield of 36 % (11 mg). H NMR
3
(
(
400 MHz, CDCl
3
): δ = 9.27 (s, 1H), 8.46 (overlapping d, 2H), 8.32 the Israel Science Foundation. D.G.C. acknowledges Z.G., the
overlapping d, 2H), 7.32 (unresolved t, 2H, pyridine‐H), 6.66 (broad Schulich Faculty of Chemistry, Technion‐Israel Institute of
1
9
t, 4H, pyridine‐H), 5.32 (broad s, 4H, pyridine‐H). F NMR (377 MHz,
CDCl ): δ = ‐48.54 (q, J = 12.07 Hz , 3F), ‐50.32 (q, J = 11.77 Hz , 3F), ‐
5
Technology, and support from KAIST for facilitating his
sabbatical year.
3
2.92 (s, 3F), ‐137.70 (m, 2F, ortho‐F), ‐138.15 (m, 4F, ortho‐F), ‐
1
52.43 (t, J = 22.28 Hz , 2F, para‐F), ‐152.66 (t, J = 21.70 Hz , 1F, para‐
‐
F), ‐161.51 (m, 2F, meta‐F), ‐163.17 (m, 4F, meta‐F). MS (APCI,
References
negative mode) for C40
024.0003 (observed). MS (APCI, positive mode) for C40
m/z = 1024.9979 (calculated), 1024.9583 (observed).
H
5
+
F
24
N
4
Al: m/z = 1023.9945 (calculated),
1
5 24 4
H F N
Al:
1
(a) S. Fukuzumi. et al, Green. Chem., 2018, 20, 948‐963; (b) X.
Dai, D. W. Chen, W. Y. Zhou. et al, Cat. Commun., 2018, 17,
8
1
5‐89; (c) C. M. White, J. P. Zhao, J. Am. Chem. Soc., 2018, 140,
3988‐14009; (d) J. Jiang, J.‐X. Wang, X.‐T. Zhou. et al, Chem.
Synthesis of 4CF
0.23 g, 1.2 mmol) were dissolved in 5‐10 mL DMF which was sparged
with argon after 5 min. The reagent methyl–2,2–difluoro–2–
fluorosulfonyl) acetate (FSO CF CO Me) (0.16 mL, 1.2 mmol) was
then added into the reaction. The temperature of the reaction
mixture was maintained at 100 ℃. The reaction was monitored by
TLC, after an ample time of 10 h, the reaction mixture was then
quenched and separated with water and CH Cl (1:1 by volume); then
2 2
the organic phase was evaporated. The greenish crude product was
purified by silica gel chromatography with ethyl acetate and hexane
3
‐Al. A dry portion of 4I‐Al (40 mg, 30 μmol) and CuI
Eur. J., 2018, 23, 2666‐2674; (e) F. Burg, M. Gicquel, S.
Breitenlechner. et al, Angew. Chem. Int. Ed., 2018, 57, 2953‐
2
1
(a) P. Adler, C. J. Teskey, D. Kaiser, M. Holy, H. H. Sitte and N.
Maulide, Nat. Chem., 2019, 329‐334; (b) C. Varlow, D. Szames,
K. Dahl, V. Bernard‐Gauthier and N. Vasdev, Chem. Commun.,
(
957; (f) G. Li. et al, Angew. Chem. Int. Ed., 2018, 57, 1251‐
255.
(
2
2
2
2
3
2
018, 54, 11835‐11842; (c) E. P. Gillis, K. J. Eastman, M. D. Hill,
D. J. Donnelly and N. A. Meanwell, J. Med. Chem., 2015, 58,
8
315‐8359; (d) Q. Shen, Y.‐G. Huang, C. Liu, J.‐C. Xiao, Q. Y.
Chen, Y. Guo. J. Fluor. Chem., 2015, 179, 14‐22.
(
1:2 by volume) as the mobile phase. The fluorescent parts were
collected and precipitated/recrystallized by CH Cl and hexane (1:1
‐Al were obtained
): δ = 8.10 (d, JH‐
(a) V. S. Barata, A. Postigo, Coord. Chem. Rev., 2013, 257,
2
2
3
8
4
051‐3069. (b) A. Studer, Angew. Chem. Int. Ed., 2012, 51,
950‐8958. (c) D. A. M. McClinton. et al, Tetrahedron., 1992,
8, 6555‐6566.
by volume); importantly, a pure green solid 4CF
3
1
with a yield of 42% (14 mg). H NMR (400 MHz, C
6
D
6
H
= 4.89 Hz, 2H), 7.91 (d, JH‐H = 4.88 Hz, 2H), 7.36 (s, 1H, pyridine‐H),
4
5
R. W. Taft, Chem. Rev., 1991, 91, 165‐195.
1
9
5
.62 (broad s, 2H, pyridine‐H), 5.11 (broad s, 2H, pyridine‐H)). F
): δ = ‐49.23 (s, 6F), ‐49.30 (s, 6F ), ‐138.72 (m,
F, ortho‐F), ‐150.09 (t, JF‐F = 21.70 Hz, 1F, para‐F), ‐150.30 (t, JF‐F
(a) O. Wagner, J. Thiele, M. Weinhart, L. Mazutis, D. A. Weitz,
R. Haag. Lab. Chip., 2016, 16, 65‐69; (b) M. A. Miller and E. M.
Sletten, Org. Lett., 2018, 20, 6850–6854; (c) H. Wang, J. J. Hu,
X. P. Cai, J. R. Xiao and Y. Y. Cheng, Polym. Chem., 2016, 7,
2319‐2322; (d) C.‐U. Lee, R. Khalifehzadeh, B. Ratner and A. J.
Boydston, Macromolecules., 2018, 51, 1280‐1289.
6 6
NMR (377 MHz, C D
6
=
2
1.01 Hz, 2F, para‐F), ‐160.74 (m, 2F, meta‐F), ‐162.55 (m, 4F, meta‐
‐
F). MS (APCI, negative mode) for C41
H
4
F
27
N
4
Al: m/z = 1091.9815
+
(
calculated), 1091.9836 (observed). MS (APCI, positive mode) for
Al: m/z = 1092.9893 (calculated), 1092.9815 (observed).
6
(a) G. Valero, X. Companyó, R. Rios, Chem. Eur. J., 2011, 17,
41 4 27 4
C H F N
2
6
4
018‐2037. (b) J. A. Ma and D. Cahard, Chem. Rev., 2004, 104,
119‐6146. (c) J. A. Ma and D. Cahard, Chem. Rev., 2008, 108,
203‐4278.
Crystal Data for 3I‐Al: moiety formula: 4(C47
sum formula: C203 27, M = 5662.63; orthorhombic, space
group P2 (19), a = 16.5663(1) Å, b = 22.8606(1) Å, c = 26.4461(1)
Å, V = 10015.55(8) Å , Z = 2, T = 100 K, D
15.778, Data completeness = 1.83/0.99, θ(max)= 74.504, R
reflections) = 0.0463 (19527), wR (reflections) = 0.1190 (20347), S
1.037, Npar = 1421, CCDC code: CCDC1868043.
3 6 5 5
H15AlF15I N ), 3(C H N);
7
8
X. Zhan. et al, Inorg. Chem., 2019, 58, 6184‐6198.
4 60 12
H75Al F I N
(a) Y. Kobayashi, I. Kumadaki and S. Kuboki, J. Fluor. Chem.,
1 1 1
2 2
1
982, 19, 517‐520. (b) J. Leroy, J. Fluor. Chem., 1991, 53, 61‐
3
‐3
‐1
c
= 1.87757 g cm , µ (mm )
70. (c) K. E. Thomas, L. J. McCormick. et al, Angew. Chem.‐Int.
Edit., 2017, 56, 10088‐10092. (d) S. Shimizu, N. Aratani and A.
Osuka, Chem.‐Eur. J., 2006, 12, 4909‐1918. (e) Y. Terazono and
D, Dolphin, J. Org. Chem., 2003, 68, 1892‐1900. (f) S. Kang. et
al, Chem.‐Asian J., 2008, 3, 2065‐2074.
=
(
2
=
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1‐3 | 7
Please do not adjust margins

Plea sDe a dl t oo nn oT tr aa nd sj au cs tt i om n as rgins
Page 8 of 9
View Article Online
DOI: 10.1039/C9DT02150G
ARTICLE
Journal Name
9
1
(a) E. T. Kolle, H. Ingar and A. Ghosh, Inorg.Chem., 2008, 47,
0469‐10478; (b) E. T. Kolle, C. Jeanet and A. Ghosh, Inorg.
Chem., 2011, 50, 3247‐3251.
0 (a) A. Mahammed, B. Mondal, A. Rana and Z. Gross, Chem.
Commun., 2014, 50, 2725‐2727; (b) L. Wagnert, R. Rubin, A.
Berg, A. Mahammed, Z. Gross and H. Levanon, J. Phys. Chem.
B., 2010, 114, 14303‐14308.
1
1
1
1
1 Q. C. Chen, M. Soll, A. Mizrahi, I. Saltsman, N. Fridman, M.
Saphier and Z. Gross, Angew. Chem.Int. Ed., 2018, 57, 1006‐
1
010.
2 K. Sudhakar, A. Mizrahi, M. Kosa, N. Fridman, B. Tumanskii, M,
Saphier and Z. Gross, Angew. Chem. Int. Ed., 2017, 56, 9837‐
9
841.
3 (a) K. Rybicka‐Jasinska, W. Q. Shan, K. Zawada, K. M. Kadish
and D. Gryko, J. Am. Chem. Soc., 2016, 138, 15451‐15458; (b)
K. Rybicka‐Jasińska and D. Gryko, Eur. J. Org. Chem., 2017,
2
104‐2107;(c) M, Giedyk, K. Goliszewska and D. Gryko, Chem.
Soc. Rev., 2015, 44, 3391‐3404.
1
1
4 J. Vestfrid, I. Goldberg and Z. Gross, Inorg. Chem., 2014, 53,
1
0536‐10542.
5 (a) N. Miyaura, A. Suzuki, Chem. Rev., 1995, 95, 2457‐2483; (b)
R. F. Heck, J. P. Nolley, J. Org. Chem., 1972, 37, 2320‐2322; (c)
D. Milstein, J. K. Stille, J. Am. Chem. Soc., 1978, 100, 3636‐
3
638. (d) A. S. Guram, S. L. Buchwald, J. Am. Chem. Soc., 1994,
16, 7901‐7902; (e) F. Paul, J. Patt, J. F. Hartwig, J. Am. Chem.
1
Soc., 1994, 116, 5969‐5970.
1
1
6 A. Mahammed and Z. Gross, Angew. Chem. Int. Ed., 2015, 54,
1
2370‐12373.
7 (a) X. P. Bao. et al, Org. Lett., 2017, 19, 5780‐5782; (b) Y. J.
Yang. et al, ACS. Appl. Mater. Interfaces., 2017, 9, 30958‐
3
3
4
0963. (c) X. T. Ma and S. K. Tian, Adv. Synth. Catal., 2013, 355,
37‐340. (d) R. K. Chinnagolla. et al, Chem. Commun., 2013,
9, 3146‐3148.
1
1
8 a) K. Ohkubo, A. Fujimoto and S. Fukuzumi, J. Am. Chem. Soc.,
013, 135, 5368‐5371; (b) K. Ohkubo, T. Kobayashi and S.
2
Fukuzumi, Angew. Chem. Int. Ed., 2011, 50, 8652‐8655; (c) H.
Kotani, K. Ohkubo and S. Fukuzumi, J. Am. Chem. Soc., 2004,
1
26, 15999‐16006; (d) K. Ohkubo, K. Mizushima, R. Iwata and
S. Fukuzumi, Chem. Sci., 2011, 2, 715‐722; (e) S. Fukuzumi and
K. Ohkubo, Org. Biomol. Chem., 2014, 12, 6059‐6071.
9 N. V. Klassen, D. Marchington and H. C. E. McGowan, Anal.
Chem., 1994, 66, 2921‐2925.
8
| J. Name., 2012, 00, 1‐3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 9
Dalton Transactions
View Article Online
DOI: 10.1039/C9DT02150G
2
50x242mm (96 x 96 DPI)