Synthesis and characterization of meso-to-meso directly linked porphyrin-diazaporphyrin triads

Article abstract of DOI:10.1142/S1088424618500633

Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of reactions including formylation via Vilsmeier-Haack reaction, condensation with pyrrole, bromination with N-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), metallated cyclization of dibromodipyrrin-metal complexes with NaN3 and demetalization. All these triads were comprehensively characterized by 1H NMR, high-resolution mass spectrometry and UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)° between each mean plane of porphyrin and that of central diazaporphyrin The UV-vis absorption spectra disclosed that the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm, respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin monomers reported previously the molar extinction coefficients, particularly for triad 8Ni are much higher.

Full text of DOI:10.1142/S1088424618500633

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2018; 22: 1–7
DOI: 10.1142/S1088424618500633
Published at http://www.worldscinet.com/jpp/
Synthesis and characterization of meso-to-meso directly
linked porphyrin-diazaporphyrin triads
Yingying Jia, Ling Xu, BangshaoYin, Mingbo Zhou*, and Jianxin Song*◊
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China),
Key Laboratory of Application and Assemble of Organic Functional Molecules, Hunan Normal University,
Changsha 410081, China
Dedicated to Professor Naisheng Chen on the occasion of his 80th birthday
Received 21 March 2018
Accepted 20 April 2018
ABSTRACT: Beginning with 5,10,15-triarylporphyrin-nickel complex, five meso-to-meso directly
linked porphyrin-diazaporphyrin triads were successfully prepared for the first time through a series of
reactions including formylation via Vilsmeier–Haack reaction, condensation with pyrrole, bromination
with N-Bromosuccinimide (NBS), oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ),
metal-templated cyclization of dibromodipyrrin-metal complexes with NaN3 and demetalization. All
1
these triads were comprehensively characterized by H NMR, high-resolution mass spectrometry and
UV-vis absorption. In addition, the structure of compound 6Ni was unambiguously determined by X-ray
diffraction analysis, which showed that the two dihedral angles are both 86.65 (4)° between each mean
plane of porphyrin and that of central diazaporphyrin. The UV-vis absorption spectra disclosed that
the longest wavelengths of Soret bands and Q bands for these triads were observed at 429 and 642 nm,
respectively. In contrast to diazaporphyrin-porphyrin dyads, diazaporphyrin dimers and diazaporphyrin
monomers reported previously, the molar extinction coefficients, particularly for triad 8Ni, are much
higher.
KEYWORDS: porphyrin, 5,15-diazaporphyrin, triads, p-conjugation.
at 5,15 positions can form a class of chromophores that
INTRODUCTION
are known as 5,15-diazaporphyrins (DAPs). They possess
Porphyrin arrays have attracted considerable attention
nondegenerate highest occupied molecular orbitals
inrecentyears,mainlybecauseoftheirnumerouspotential
(HOMOs) and lowest unoccupied molecular orbitals
applications in the fields of energy transfer, photodynamic
(LUMOs). Moreover, after incorporation of two meso-
therapy (PDT), pigments, and light-harvesting models
nitrogen atoms, the molecular configuration becomes a
[1–5]. In this extended family, meso-linked arrays are
usually constructed via ethyne-bridged [2], butadiyne-
D2h symmetry. Due to the intense and red-shifted Q bands
resulting from their intrinsic properties, DAPs attract
bridged [3], aromatics-bridged [4], as well as fused
continuing and much higher interest in relation to any
porphyrin arrays [5], which exhibit unusual properties that
of the other partial azaporphyrins [6]. Compared with
stem from their unique p-conjugated system. Replacing
two methine carbons of porphyrins with nitrogen atoms
the rich chemistry of porphyrins and phthalocyanines,
however, DAPs are rarely explored, which could be
attributed to synthetic difficulties during the process of
peripheral modification and cyclization of the core in
◊ꢀSPP full member in good standing
DAPs. Since Shinokubo’s and Matano’s groups reported
*Correspondence to: Mingbo Zhou, tel/fax: +86-0731-88872
the synthesis of b-unsubstituted MDAPs complexes
(M metal) independently [7], b-functionalized
618, email: zhoumingbo@hunnu.edu.cn; Jianxin Song, tel/
fax: +86-0731-88872618, email: jxsong@hunnu.edu.cn.
=
Copyright © 2018 World Scientific Publishing Company

2
Y. JIA ET AL.
MDAP derivatives were gradually obtained [8–13]. For
example, Shinokubo et al. demonstrated the synthesis
and application of 3-(2-pyridyl)-NiDAPs, which could
act as an external N,N-chelating ligand for PtII, RuII, and
ReI ions [9]. Subsequently, coupling of b-bromo-MDAPs
with arylboronic acids by means of palladium-catalyzed,
ten b-aryl-MDAPs were synthesized by Matano and
co-workers [10]. Very recently, the same group reported
the direct amination of b-unsubstituted DAPs with
secondary and primary amines to yield b-mono or tetra-
aminosubstituted-DAPs, regioselectively[11].Allstudies
disclosed that these b-substituted MDAPs exhibited red-
shifted absorption/emission bands compared to their
precursors. On the other hand, covalently directly linked
MDAP dimers, porphyrin-ZnDAP dyads and other
groups-bridged MDAP dimers were also afforded from
b-bromo MDAPs [12–13]. For instance, Matano and
Lemmetyinen successfully constructed the b–b directly
linked DAP dimers whose geometry was coplanar,
which resulted in extended p-systems [13]. Although
recent progress has been established for preparation of
b-functionalized MDAP derivatives by cross-coupling
reactions, scalable synthesis of diazaporphyrin-based
triads, even multi-tuples, remains a major challenge. In
addition, the structure–property relationships between
diazaporphyrin and porphyrin in these hybrids have
not been studied systematically. In recent years, one of
our research interests has focused on the synthesis and
properties of porphyrin arrays [14]. As an extension of
our previous studies, we report herein the synthesis,
structures, and UV-vis absorption properties of five new
meso-to-meso directly linked porphyrin-diazaporphyrin
triads. 1H NMR spectra of the examined compounds are
available in the supporting information, Figs S1–S7.
RESULTS AND DISCUSSION
Synthesis and characterization
The preparation of these meso-to-meso directly linked
porphyrin-diazaporphyrin triads shown in Scheme 1
was carried out according to the reported procedure
[15, 6 (h), 7]. Formylation of 5,10,15-triarylporphyrin-
nickel complex 1Ni via Vilsmeier–Haack reaction,
followed by condensation with pyrrole in the presence of
trifluoroacetic acid generated dipyrromethane 2Ni in 63%
yield. b-Bromo dipyrromethane was readily synthesized
by regioselective bromination of 2Ni with NBS in dry
tetrahydrofuran (THF) at -78°C. Subsequently, through
oxidation of this a-bromo-dipyrromethane by DDQ, the
important intermediate 3Ni was obtained in 70% yield.
The metal-templated cyclization precursors 4Ni and 5Zn
were synthesized by reaction of 3Ni with corresponding
metal salts in nearly quantitative yields. In the presence
of CuI and N,N-dimethylformamide (DMF), after reflux
for about 1 h, 4Ni and 5Zn could be converted into triads
6Ni in 35% yield and 7Zn in 12% yield, respectively.
It is noteworthy that the metal was still retained in the
diazaporphyrin core after demetalization of 6Ni with
concentrated H2SO4, nevertheless, the metal porphyrin
moieties were transformed into the corresponding
free-base derivatives. The net result was that 8Ni was
generated in 84% yield. Despite all our efforts to
Ar
Ar
Ar
Ar
Ar
Br
Br
Br
NH
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
N
NH
NH
ii
i
iii
Ar
Ni
Ar
Ni
Ar
Ni
Ar
Ni
Ar
M
Ni
Ar
Ar
Ar
N
N
Br
Br
Br
Ar
Ar
4M, M = Ni
5M, M = Zn
3Ni
1Ni
2Ni
Ar
Ar
Ar
Ar
N
N
NH
N
N
N
N
N
N
N
N
N
NH
N
N
N
N
N
N
N
N
N
N
iv
v
Ar
Ar
Ni
Ni
Ar
Ni
Ar
M
N
Ar
Ar
HN
N
HN
N
Ar
Ar
6M, M = Ni
7M, M = Zn
8Ni
Ar
Ar
Ar
Ni
Ar
Ar
Ni
Ar
N
N
N
tBu
N
NH
N
NH
N
NH
N
N
N
NH
N
N
N
N
N
vi
v
Ar
Ar =
Ar
Ar
3Ni
Ar
HN
HN
N
N
HN
N
N
tBu
HN
N
N
Ar
Ar
9Ni
10
Scheme 1. Synthetic procedure for porphyrin-azaporphyrin triads: (i) (a) POCl3, DMF, CH2Cl2, reflux; (b) TFA, pyrrole, r.t.;
(ii) (a) NBS, THF, -78°C; (b) DDQ; (iii) M(OAc)2, CH2Cl2/CH3OH, r.t. (M = Ni or Zn); (iv) NaN3, CuI, DMF, argon, reflux;
(v) Conc. H2SO4, CH2Cl2, r.t.; (vi) NaN3, Pb(acac)2, DMF, argon, reflux
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 2–7

SYNTHESIS AND CHARACTERIZATION OF meso-to-meso DIRECTLY LINKED PORPHYRIN-DIAZAPORPHYRIN TRIADS
3
demetallate 7Zn, however, no 8Zn could be isolated.
Another strategy was employed in order to synthesize
full free-base porphyrin-diazaporphyrin triads 10.
Through incorporation of 3Ni with NaN3 in the presence
of Pb(acac)2, 9Ni was afforded as a brown gray solid
in 4% yield. After demetallation, compound 10 was
achieved in 62% yield. The HR-ESITOF mass spectrum
of this free-base triad exhibited the parent-ion peak at
m/z = 2059.25 (calcd for C142H157N14 [M]+: = 2059.27),
which was consistent with the molecular structure of 10.
In 1H NMR spectra, the pyrrolic NH protons of 9Ni and
8Ni appeared at d = -1.70 and -2.11 ppm, respectively
(Figs S5 and S6). This means the magnetic shielding
effects at the core of the diazaporphyrin ring are weaker
than those of the porphyrin ring. Similarly, the magnetic
shielding effects also occur in compound 10; its two
kinds of pyrrolic NH protons were observed at d = -1.50
ppm for diazaporphyrin and -2.07 ppm for porphyrin,
respectively (Fig. S7) [6 (h)].
(a)
(b)
To our delight, single crystal of 6Ni was obtained by
the slow diffusion of CH3OH vapor into its chlorobenzene
solution. The molecular structure was unambiguously
elucidated by X-ray crystallography (Fig. 1) [16]. For
the NiDAP core, its two sets of Ni–N bond lengths are
1.904(4) and 1.920 (4) Å. The distances of N (meso)–N
(meso)′ and C (meso)–C (meso)′ are 6.741 (8) and
6.763 (9) Å, respectively. The maximum displacements
of the b-carbons, meso-carbons and meso-nitrogens
from the azaporphyrin mean plane, which is composed
of carbon and nitrogen atoms (in a 24 atom system) are
0.057 (4), 0.071 (4) and 0.036 (4) Å, which indicates that
NiDAP adopts a highly planar geometry. In addition,
with Ni–N bond lengths of 1.922 (3)–1.941 (3) Å, the
porphyrin core is slightly ruffled, which is often observed
in nickel porphyrins. The maximum displacements of the
meso-carbons and b-carbons from the porphyrin mean
plane constituted by carbon and nitrogen atoms (24
atom system) are 0.524 (4) and 0.382 (5) Å, respectively.
As shown in Fig. 1, two porphyrin rings are almost
perpendicular to the plane defined by the diazaporphyrin,
and both dihedral angles are 86.65 (4)º. Furthermore, the
bond lengths between the NiDAP and porphyrin in 6Ni
[1.502 (6) Å] closely resemble those between the NiDAP
and meso-aryl rings [1.506 (3)–1.507 (3) Å] published by
Matano et al. [10].
Ar
Ni
Ar
Ar
Ni
Ar
b a a'
N
b'
g'
c'
d'
c
g
α
N1
N
d
e
f'
f
N
N
N
N
N
N
N
N
e'
Ar
δ
N2
Ni
β
Ar
h'
h
γ
N2'
N
(c)
Bond Distance (Å) Bond
Distances (Å)
a
b
c
d
1.324 (7)
1.328 (6)
1.441 (6)
1.439 (7)
1.345 (7)
1.343 (7)
1.440 (7)
1.433 (7)
e
f
1.382 (7)
1.385 (7)
1.379 (6)
1.378 (6)
1.378 (6)
1.362 (6)
1.502 (6)
1.502 (6)
2.714 (6)
2.694 (5)
′
′
′
′
′
′
′
′
g
h
Ni-N1 1.904 (4)
Ni-N2 1.920 (4)
Angle Degree
120.4 (4)
N1-N2
N2-N
′
Angle
Degree
Optical spectroscopy
89.56 (16)
90.44 (16)
To investigate the optical properties, the UV-vis
absorption spectra of compounds 6Ni, 7Zn, 8Ni, 9Ni and
10 were measured in CHCl3 (Fig. 2), and the absorption
data are summarized in Table 1. According to these
results, conclusions can be drawn as follows: (1) in
contrast to triads 6Ni, 7Zn and 8Ni, both the Soret bands
and Q bands of free-base counterparts 9Ni and 10 are red
shifted. (2) Compared to NiDAP triads 6Ni and 8Ni, the
122.5 (4)
Fig. 1. Crystal structure and selected bond lengths and angles of
6Ni. (a) Side view and (b) top view (50% probability ellipsoids).
Hydrogen atoms and tert-butyl groups are omitted for clarity:
gray (C), blue (N), green (Ni). (c) The structure of compound
6Ni. Ar = 3,5-di-tert-butylphenyl
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 3–7

4
Y. JIA ET AL.
8Ni, 9Ni and 10 were successfully prepared via a series
of transformations from 5,10,15-triarylporphyrin-nickel
complex. In addition, all of these triads were comprehen-
1
sively characterized by H NMR, high-resolution mass
spectrometry and UV-vis absorption. The structure of
6Ni was confirmed using X-ray diffraction analysis, and
both porphyrin rings are almost perpendicular to the
diazaporphyrin plane. These porphyrin-diazaporphyrin
arrays exhibit different optical properties compared to
DAP monomers, such as remarkable red-shifted Soret
bands and Q bands, as well as higher molar extinction
coefficients. Further studies on oxidation of conjugated
porphyrin-diazaporphyrin triads, electron transfer, and
other photophysical and electrochemical properties are still
in progress. The fundamental results achieved from this
study will be useful for the rational design and synthesis of
new classes of diazaporphyrin-based functional molecules
for application in optoelectronics, biomimetic catalysts,
and other fields.
Fig. 2. UV-vis/NIR absorption spectra of 6Ni (black line), 7Zn
(red line), 8Ni (dark cyan line), 9Ni (blue line) and 10 (purple
line) in CHCl3
Table 1. UV-vis absorption data of
triads
EXPERIMENTAL
Compound
6Ni
lmax/nm
421, 534, 563, 612
425, 528, 565, 624
423, 514, 608
Materials and equipment
7Zn
1H NMR (500 MHz) spectra were recorded on a
Bruker AVANCE-500 spectrometer, and chemical
shifts were reported on the delta scale in ppm relative
to CHCl3 as an internal reference (d = 7.260 ppm).
UV-vis absorption spectra were recorded on a Shimadzu
UV-3600 spectrometer. High resolution mass spectra
were obtained with a Bruker ultrafleXtreme MALDI-
TOF/TOF-MS with a DCTB matrix. Unless otherwise
noted, materials obtained from commercial suppliers
were used without further purification.
X-Ray data were taken on an Agilent SuperNova
X-Ray diffractometer equipped with a large area CCD
detector, and graphite-monochromated Cu Ka radiation
(l = 1.54184 Å) was used. The crystal was kept at 103
(2) K during data collection. Using Olex2, the structure
was solved with the SHELXS structure solution program
and refined with the SHELXL refinement package using
least-squares minimization. Refinement was performed
on F2 anisotropically for all of the non-hydrogen atoms
by the full-matrix least-squares method. The hydrogen
atoms were placed at the calculated positions and were
included in the structure calculation without further
refinement of their parameters.
8Ni
9Ni
426, 653
10
429, 515, 551, 642
others exhibit weaker absorption. (3) Both Soret bands
and their Q bands of these triads are more significantly
intense and red shifted than reported DAP monomers
[10]. For example, free-base triad 10 is characterized
by maximum absorption values of the Soret band and
Q bands at 429 and 642 nm, which extend 36 and 15 nm,
respectively, compared to free-base 5,15-diaza-10,20-
dimesitylporphyrins. This can be explained by the nature
of porphyrins, as a larger p-electron conjugated system
relative to mesityl compounds, which could further
expand the p-electronic network of arrays. (4) Due to their
weaker coplanarization, all these directly linked meso-
to-meso triads are of shorter wavelengths of Q bands
vs. those of b–b directly linked bis-NiDAP, in which
two rings are nearly in the same plane [13]. (5) Their
molar extinction coefficients increase more remarkably
than for DAP dyads and monomers reported previously.
Particularly, the e value of 8Ni, is much higher than any
other known diazaporphyrin derivatives.
General procedures
Synthesis of 3Ni. Compound 2Ni (322.8 mg, 0.3 mmol)
was dissolved in dry THF (40 mL) and cooled to -78°C.
The resulting mixture was stirred for about 15 min. NBS
(4.0 g, 22 mmol) was added in two portions over 1 h with
monitoringbyTLC.Afterthereactionwascomplete, DDQ
(2.60 g, 11.4 mmol) in THF (15 mL) was added dropwise
CONCLUSION
In summary, five novel meso-to-meso directly linked
porphyrin-diazaporphyrin triads, namely, 6Ni, 7Zn,
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 4–7

SYNTHESIS AND CHARACTERIZATION OF meso-to-meso DIRECTLY LINKED PORPHYRIN-DIAZAPORPHYRIN TRIADS
5
over 10 min. The resulting mixture was stirred at room
temperature with monitoring by TLC. Then evaporation
of the solvent under reduced pressure, followed by silica
gel column chromatography (using n-hexane as an eluent)
and recrystallization from CH2Cl2/CH3OH gave 3Ni as a
yellow solid (229.5 mg, 0.03 mmol, 62% yield).
aqueous NaHCO3 solution and water. The organic layer
was dried over Na2SO4. Then the solvent was evaporated
under reduced pressure, followed by silica-gel column
chromatography (n-hexane/CH2Cl2 as eluent). The
residue was recrystallized from CH2Cl2/CH3OH to obtain
8Ni as a green solid (16 mg, 0.0076 mmol, 84.4% yield).
1H NMR (500 MHz, CDCl3): d = 9.06 (d, 4H, J = 5 Hz,
b-H), 9.01 (d, 4H, J = 4.5 Hz, b-H), 8.98 (d, 4H, J =
4.5 Hz, b-H), 8.76 (d, 4H, J = 4.5 Hz, b-H), 8.43 (d,
4H, J = 5 Hz, b-H), 8.17 (d, 4H, J = 1.5 Hz, Ar-o-H),
8.13 (d, 8H, J = 1.5 Hz, Ar-o-H), 8.05 (s, 4H, J = 4.5 Hz,
b-H), 7.86 (m, 2H, J = 1.5 Hz, Ar-p-H), 7.76 (s, 4H,
J = 1.5 Hz, Ar-p-H), 1.58 (s, 36H, t-Bu-H), 1.49 (s, 72H,
Synthesisof4Ni.Compound3Ni(246.8mg,0.2mmol)
was dissolved in CH2Cl2 (12 mL) and CH3OH (9 mL),
.
then Ni(OAc)2 4H2O (24.9 mg, 0.1 mmol) was added.
The mixture was stirred at room temperature for about
5 h. Evaporation of the solvent under reduced pressure,
followed by GPC and silica-gel column chromatography
(CH2Cl2/n-hexane as an eluent) and recrystallization with
CH2Cl2/CH3OH, 4Ni was obtained as a dark red solid
(242.0 mg, 96%).
t-Bu-H), -2.11 (s, 4H, NH) ppm; UV-vis (CHCl3): lmax
-1
(e [M-1 cm ]) = 423 (459000), 514 (45600), 608
.
.
Synthesis of 5Zn. Replacement of Ni(OAc)2 4H2O
(137500) nm; MALDI-TOF-MS (positive mode): m/z =
2115.27 [M]+, calcd for (C142H155N14Ni)+ = 2116.19.
Synthesis of 9Ni. A mixture of 3Ni (246.8 mg,
0.2 mmol), Pb(acac)2 (48.6 mg, 0.12 mmol), sodium azide
(28.6 mg, 0.44 mmol) and DMF (30 mL) was heated at
100°C for 1 h. Brine was added to the reaction mixture,
and the organic phase was separated, washed with water
and dried over Na2SO4. The solvent was evaporated
under reduced pressure, followed by silica-gel column
chromatography (n-hexane/CH2Cl2 as eluent) and
recrystallization from CH2Cl2/CH3OH gave 9Ni as a
.
with Zn(OAc)2 2H2O; the synthetic procedure is the same
as 4Ni. 5Zn was obtained as a dark red solid in 94% yield.
Synthesis of 6Ni. A mixture of sodium azide (51.0 mg,
0.785 mmol), CuI (149.9 mg, 0.79 mmol), and DMF
(30 mL) was stirred at room temperature until the color of
the solution changed to black. 4Ni (240.7 mg, 0.1 mmol)
was added in one portion, and the mixture was heated
at 110°C for 1 h. Brine was added, and the organic
phase was washed with water for several times and dried
over Na2SO4. Evaporation of the solvent under reduced
pressure, followed by silica-gel column chromatography
(CH2Cl2/n-hexane as an eluent) and recrystallization
with CH2Cl2/CH3OH, 6Ni was obtained as a green solid
1
brown-gray solid (15.3 mg, 0.008 mmol, 4% yield). H
NMR (500 MHz, CDCl3): d = 9.10 (d, 4H, J = 5 Hz,
b-H), 8.94 (d, 4H, J = 5 Hz, b-H), 8.90 (d, 4H, J =
5 Hz, b-H), 8.70 (d, 4H, J = 5 Hz, b-H), 8.38 (d, 4H, J =
5 Hz, b-H), 8.09 (s, 4H, J = 5 Hz, b-H), 8.00 (d, 4H,
J = 1.5 Hz,Ar-o-H), 7.94 (d, 8H, J = 1.5 Hz,Ar-o-H), 7.79
(s, 2H, J = 2Hz, Ar-p-H), 7.69 (s, 4H, J = 4 Hz, Ar-p-H),
1
(78 mg, 0.035 mmol, 35% yield). H NMR (500 MHz,
CDCl3): d = 9.02 (d, 4H, J = 5 Hz, b-H), 8.92 (d, 4H,
J = 5 Hz, b-H), 8.88 (d, 4H, J = 5 Hz, b-H), 8.70 (d, 4H, J =
5 Hz, b-H), 8.37 (d, 4H, J = 5 Hz, b-H), 8.03 (d, 4H, J =
5 Hz, b-H), 7.98 (d, 4H, J = 1.5 Hz, Ar-o-H), 7.93 (d, 8H,
J = 1.5Hz, Ar-o-H), 7.77 (t, 2H, J = 2 Hz, Ar-p-H), 7.68
1.54 (s, 36H, t-Bu-H), 1.44 (s, 72H, t-Bu-H), -1.69 (s,
-1
2H, NH) ppm; UV-vis (CHCl3): lmax (e [M-1 cm ]) =
.
(t, 4H, J = 4Hz, Ar-p-H), 1.53 (s, 36H, t-Bu-H), 1.44 (s,
335 (29900), 426 (234800), 653 (44700) nm; MALDI-
TOF-MS (positive mode): m/z = 2172.04 [M]+, calcd for
(C142H153N14Ni2)+ = 2173.11.
-1
72H, t-Bu-H) ppm; UV-vis (CHCl3): lmax (e [M-1 cm ]) =
.
421 (336600), 534 (36400), 563 (41500), 612 (99300)
nm; MALDI-TOF-MS: m/z = 2227.83, calcd for
(C142H150N14Ni3) = 2228.03.
Synthesis of 10. Replacement of 6Ni with 9Ni; the
synthetic procedure is the same as 8Ni. 10 was obtained
as a gray solid in 62% yield. 1H NMR (500 MHz, CDCl3):
d = 9.14 (d, 4H, J = 5 Hz, b-H), 9.03 (d, 4H, J = 5 Hz,
b-H), 8.99 (d, 4H, J = 5 Hz, b-H), 8.76 (d, 4H, J = 5 Hz,
b-H), 8.43 (d, 4H, J = 5 Hz, b-H), 8.18 (s, 4H, J =
5 Hz, b-H), 8.14 (d, 8H, J = 1.5 Hz, Ar-o-H), 8.11 (d,
4H, J = 1.5 Hz, Ar-o-H), 7.86 (s, 2H, J = 2 Hz, Ar-p-H),
7.75 (s, 4H, J = 4 Hz, Ar-p-H), 1.59 (s, 36H, t-Bu-H),
Synthesis of 7Zn. Replacement of 4Ni with 5Zn; the
synthetic procedure is the same as 6Ni. 7Zn was obtained
1
as a green solid in 12% yield. H NMR (500 MHz,
CDCl3): d = 9.15 (d, 4H, J = 5 Hz, b-H), 8.94 (d, 4H, J =
5 Hz, b-H), 8.90 (d, 4H, J = 5 Hz, b-H), 8.68 (d, 4H,
J = 5 Hz, b-H), 8.40 (d, 4H, J = 5 Hz, b-H), 8.05 (s, 4H,
J = 5 Hz, b-H), 8.00 (s, 4H, J = 1.5 Hz, Ar-o-H), 7.94 (s,
8H, J = 1.5 Hz, Ar-o-H), 7.79 (s, 2H, J = 2 Hz, Ar-p-H),
7.68 (s, 4H, J = 4 Hz, Ar-p-H), 1.54 (s, 36H, t-Bu-H),
1.48 (s, 72H, t-Bu-H), -1.50 (s, 2H, NH), -2.07 (s, 4H,
-1
NH) ppm; UV-vis (CHCl3): lmax (e [M-1 cm ]) = 429
.
1.44 (s, 72H, t-Bu-H) ppm; UV-vis (CHCl3): lmax
(278400), 515 (35500), 551 (42200), 642 (47000) nm;
MALDI-TOF-MS (positive mode): m/z = 2059.25 [M]+,
calcd for (C142H157N14)+ = 2059.27.
-1
(e [M-1 cm ]) = 425 (226700), 528 (26600), 565 (23400),
.
624 (66600) nm; MALDI-TOF-MS: m/z = 2235.98, calcd
for (C142H150N14Ni2Zn) = 2235.02.
Synthesis of 8Ni. To a solution of 6Ni (10 mg,
0.005 mmol) in CH2Cl2 (10 mL) was added concentrated
sulfuric acid (about 8 drops, 0.5 mL). The mixture was
stirred at room temperature for 1 h, and then washed with
Acknowledgments
The work is supported by the National Nature Science
Foundation of China (Grant Nos. 21602058, 21772036,
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 5–7

6
Y. JIA ET AL.
21702057), and the Scientific Research Fund of Hunan
Provincial Education Department (Grant No. 16A125).
We thank Dr. Prof. Maeda at Ritusmekan University for
HRMS Analysis, and Dr. Prof. Naoki Aratani at Nara
Institute of Science and Technology for the help with
crystal analysis.
Aratani N, Shinokubo H and Osuka A. Chem. —
Eur. J. 2010; 16: 13320–13324; (c) Maeda C,
Shinokubo H and Osuka A. Org. Lett. 2010; 12:
1820–1823. (d) Fujisawa K, Satake A, Hirota S and
KobukeY. Chem. —Eur. J. 2008; 14: 10735–10744.
(e) Regehly M, Wang T, Siggel U, Fuhrhop JH and
Röder B. J. Phys. Chem. B 2009; 113: 2526–2531.
(f) Maeda C, Shinokubo H and Osuka A. Org. Lett.
2009; 11: 5322–5325.
Supporting information
1H NMR spectra of the examined compounds are given
in the supplementary material. This material is available
free of charge via the Internet at http://www.worldscinet.
com/jpp/jpp.shtml.
Crystallographic data have been deposited at the
Cambridge Crystallographic Data Centre (CCDC) under
number CCDC-1838476. Copies can be obtained on
request, free of charge, via http://www.ccdc.cam.ac.uk/
data_request/cif or from the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK
(fax: +44 1223-336-033 or email: deposit@ccdc.cam.
ac.uk).
5. For selected examples, see: (a) Pawlicki M, Morisue
M, Davis NKS, McLean DG, Haley JE, Beuerman E,
Drobizhev M, Rebane A, Thompson AL, Pascu SI,
Accorsi G, Armaroli N and Anderson HL. Chem. Sci.
2012; 3: 1541–1547. (b) Zeng W, Ishida M, Lee S,
Sung YM, Zeng Z, Ni Y, Chi C, Kim D and Wu J.
Chem. —Eur. J. 2013; 19: 16814–16824. (c) Bren-
nan BJ, Arero J, Liddell PA, Moore TA, Moore AL
and Gust D. J. Porphyrins Phthalocyanines 2013; 17:
247–251. (d) Brennan BJ, Kenney MJ, Liddell PA,
Cherry BR, Li J, Moore AL, Moore TA and Gust D.
Chem. Commun. 2011; 47: 10034–10036. (e) Ikeda T,
Aratani N, Easwaramoorthi S, Kim D and Osuka A.
Org. Lett. 2009; 11: 3080–3082. (f) SahooAK, Naka-
mura Y, Aratani N, Kim KS, Noh SB, Shinokubo H,
Kim D and Osuka A. Org. Lett. 2006; 8: 4141–4144.
(g) Feng CM, ZhuYZ, Zhang SC, ZangY and Zheng
JY. Org. Biomol. Chem. 2015; 13: 2566–2569.
6. (a) Matano Y. Chem. Rev. 2017; 117: 3138–3191.
(b) Kobayashi N. In The Porphyrin Handbook, Vol.
2, Kadish KM, Smith KM and Guilard R. (Eds.)
Academic Press: San Diego, CA, 2000; pp. 301–
360. (c) Mack J and Kobayashi N. Chem. Rev.
2011; 111: 281–321. (d) Ogata H, Fukuda T, Nakai
K, Fujimura Y, Neya S, Stuzhin PA and Kobayashi
N. Eur. J. Inorg. Chem. 2004; 1621–1629. (e) Pan
N, Bian Y, Yokoyama M, Li R, Fukuda T, Neya S,
Jiang J and Kobayashi N. Eur. J. Inorg. Chem. 2008;
5519–5523. (f) Mack J, Sosa-Vargas L, Coles SJ,
Tizzard GJ, Chambrier I, Cammidge AN, Cook MJ
and Kobayashi N. Inorg. Chem. 2012; 51: 12820–
12833. (g) Andrianov DS, Rybakov VB and Che-
prakov AV. Chem. Commun. 2014; 50: 7953–7955.
(h) Matano Y, Shibano T, Nakano H, Kimura Y and
Imahori H. Inorg. Chem. 2012; 51: 12879–12890.
(i) Sudoh K, Satoh T, Amaya T, Furukawa K, Mino-
ura M, Nakano H and Matano Y. Chem. —Eur. J.
2017; 23: 16364–16373. (j) Yamamoto M, Takano
Y, Matano Y, Stranius K, Tkachenko NV, Lemm-
etyinen H, Imahori H. J. Phys. Chem. C 2014; 118:
1808–1820. (k) Stuzhin PA, Khelevina OG. Coord.
Chem. Rev. 1996; 147: 41–86.
REFERENCES
1. For selected reviews, see: (a) Tanaka T and Osuka
A. Chem. Soc. Rev. 2015; 44: 943–969. (b) Naka-
mura Y, Aratani N and Osuka A. Chem. Soc. Rev.
2007; 36: 831–845. (c) Burrell AK, Officer DL,
Plieger PG and Reid DCW. Chem. Rev. 2001; 101:
2751–2796. (d) Yang J, Yoon MC, Yoo H, Kim P
and Kim D. Chem. Soc. Rev. 2012; 41: 4808–4826.
2. For selected examples, see: (a) Lin VSY, DiMagno
SG and Therien MJ. Science 1994; 264: 1105–1111.
(b) Duncan TV, Wu SP and Therien MJ. J. Am.
Chem. Soc. 2006; 128: 10423–10435. (c) Susumu
K and Therien MJ. J. Am. Chem. Soc. 2002; 124:
8550–8552. (d) Susumu K, Frail PR, Angiolillo
PJ and Therien MJ. J. Am. Chem. Soc. 2006; 128:
8380–8387. (e) Ryan A, Gehrold A, Perusitti R,
Pintea M, Fazekas M, Locos OB, Blaikie F and
Senge MO. Eur. J. Org. Chem. 2011; 5817–5844.
(f) Anabuki S, Tokuji S, Aratani N and Osuka A.
Org. Lett. 2012; 14: 2778–2781.
3. For selected examples, see: (a) Arnold DP, John-
son AW and Mahendran M. J. Chem. Soc., Perkin
Trans. 1 1978; 35: 366–370. (b) Taylor PN, Huus-
konen J, Rumbles G, Aplin RT, Williams E and
Anderson HL. Chem. Commun. 1998; 909–910. (c)
Balaz M, Collins HA, Dahlstedt E andAnderson HL.
Org. Biomol. Chem. 2009; 7: 874–888. (d) Yamada
H, Okujima T and Ono N. Chem. Commun. 2008;
2957–2974. (e) Drobizhev M, Stepanenko Y,
Rebane A, Wilson CJ, Screen TEO and Anderson
HL. J. Am. Chem. Soc. 2006; 128: 12432–12433.
4. For selected examples, see: (a) Osawa K, Song J,
Furukawa K, Shinokubo H, Aratani N and Osuka
A. Chem. Asian. J. 2010; 5: 764–767. (b) Song J,
7. (a) Horie M, Hayashi Y, Yamaguchi S and Shi-
nokubo H. Chem. —Eur. J. 2012; 18: 5919–5023.
(b) MatanoY, Shibano T, Nakano H and Imahori H.
Chem. —Eur. J. 2012; 18: 6208–6216.
8. For selected examples, see: (a) Yamaji A, Hiroto S,
Shin JY and Shinokubo H. Chem. Commun. 2013;
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 6–7

SYNTHESIS AND CHARACTERIZATION OF meso-to-meso DIRECTLY LINKED PORPHYRIN-DIAZAPORPHYRIN TRIADS
7
49: 5064–5066. (b) Kurotobi K, Kawamoto K,
Toude Y, Fujimori Y, Kinjo Y, Ito S, Matano Y and
Imahori H. Chem. Lett. 2013; 42: 725–726.
N, Tanaka T, Liu S, Osuka A, Kim D, Song J. Chem.
—Eur. J. 2016; 22: 8801–8804 (d) Zhang S, Kim
JO, Li Y, Wen B, Zhou M, Liu S, Aratani N, Xu
L, Kim D and Song J. Chem. Commun., 2017; 53:
11488–11491 (e) Chen M, Yin B, Song J. Progress
in Chemistry 2015; 27: 641–654. (f) Cai H, Fuji-
moto K, Lim JM, Wang C, Huang W, Rao Y, Zhang
S, Shi H, Yin B, Chen B, Ma M, Song J, Kim D
and Osuka A. Angew. Chem., Int. Ed. 2014; 53:
11088–11091. (g) Xu L, Wen B, Kim G, Kim T,
Cheng F, Zhou M, Xu L, Tanaka T, Yin B, Osuka A,
Kim D, Song J. Angew. Chem., Int. Ed. 2017; 56:
12322–12326. (h) Yin B, Liang X, Zhu W, Xu L,
Zhou M, Song J. Chinese Chemical Letters 2018;
29: 99–101.
9. Yamaji A, Shin JY, Miyake Y and Shinokubo H.
Angew. Chem., Int. Ed. 2014; 53: 13924–13927.
10. Omomo S, Furukawa K, Nakano N, Matano Y.
J. Porphyrins Phthalocyanines 2015; 19: 775–785.
11. Omomo S, Sugai T, Minoura M, Nakano H and
Matano Y. Angew. Chem., Int. Ed. 2018; 57:
3797–3800.
12. For selected examples, see: (a) Omomo S,
Maruyama Y, Furukawa K, Furuyama T, Nakano
H, Kobayashi N and Matano Y. Chem. —Eur. J.
2015; 21: 2003–2010. (b) Abou-Chahine F, Fujii D,
Imahori H, Nakano H, Tkachenko NV, Matano Y
and Lemmetyinen H. J. Phys. Chem. B 2015; 119:
7328–7337. (c) Kawamata M, Sugai T, Minoura M,
Maruyama Y, Furukawa K, Holstrom C, Nemykin
VN, Nakano H and MatanoY. Chem. Asian J. 2017;
12: 816–821.
13. MatanoY, Fujii D, Shibano T, Furukawa K, Nakano
H, Higashino T and Imahori H. Chem. —Eur. J.
2014; 20: 3342–3349.
14. (a) Huang W, Lee SK, SungYM, Peng F, Yin B, Ma
M, Chen B, Liu S, Kirk SR, Kim D and Song J.
Chem. —Eur. J. 2015; 21: 15328–15338. (b) Yin B,
Kim T, Zhou M, Huang W, Kim D, Song J. Org.
Lett. 2017; 19: 2654–2657. (c) RaoY, Kim JO, Kim
W, Zhong G, Yin B, Zhou M, Shinokubo H, Aratani
15. Tanaka T, Aratani N, Lim JM, Kim KS, Kim D and
Osuka A. Chem. Sci. 2011; 2: 1414–1418.
16. Crystal data for 6Ni: C178H180Cl6N14Ni3, Mw =
2904.18, triclinic, space group P-1 (no. 2), a =
9.6113 (2) Å, b = 14.8142 (3) Å, c = 27.6564
(5) Å, a = 81.0420 (17)°, b = 84.2972 (14)°, g =
85.8892 (16)°, V = 3864.21 (13) Å3, Z = 1, T =
103 (2) K, m(CuKa) = 1.818 mm-1, Dcalc = 1.248
g/cm3, 38986 reflections measured (9.262° ≤ 2Θ
≤ 127.998°), 12809 unique (Rint = 0.0658, Rsigma
=
0.0645) which were used in all calculations. The
final R1 was 0.0939 (I > 2Θꢀ(I)) and wR2 was 0.2620
(all data). CCDC number: 1838476.
Copyright © 2018 World Scientific Publishing Company
J. Porphyrins Phthalocyanines 2018; 22: 7–7