1D Columnar stacking structures in the single crystals of 5,10-diarylporphyrin metal complexes

Article abstract of DOI:10.1142/S1088424617500705

A general design of a meso-Aryl porphyrin for the formation of a 1D columnar stacking structure in the single crystal state is proposed. We found that 5,10-diphenyl-and 5,10-bis(pentafluorophenyl)porphyrin metal complexes (M = Zn, Ni) can stack in a complementary manner to form a 1D columnar stacking structure in the single crystals, while the corresponding freebase porphyrins displayed herringbone or dimeric orthogonal packing forms. The structural details of the obtained 1D columnar packing structures are discussed in comparison with precedented examples including 5,10-diphenylporphyrin Cu(II) and Ag(II) complexes, 5,10-diphenyl N-confused porphyrin Ag(III) complex and 5,10-bis(pentafluorophenyl)corrole.

Full text of DOI:10.1142/S1088424617500705

Journal of Porphyrins and Phthalocyanines
J. Porphyrins Phthalocyanines 2017; 21: 1–8
DOI: 10.1142/S1088424617500705
Published at http://www.worldscinet.com/jpp/
1D Columnar stacking structures in the single crystals
of 5,10-diarylporphyrin metal complexes
Takayuki Tanaka,a* Kento Uetaa, Shin Ikedaa, Naoki Aratanib and Atsuhiro Osukaa*
a Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa Oiwake-cho, Sakyo-ku,
Kyoto 606-8502, Japan
bGraduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5 Takayama-cho,
Ikoma 630-0192, Japan
Received 31 October 2017
Accepted 14 November 2017
ABSTRACT: A general design of a meso-aryl porphyrin for the formation of a 1D columnar
stacking structure in the single crystal state is proposed. We found that 5,10-diphenyl- and
5,10-bis(pentafluorophenyl)porphyrin metal complexes (M = Zn, Ni) can stack in a complementary
manner to form a 1D columnar stacking structure in the single crystals, while the corresponding freebase
porphyrins displayed herringbone or dimeric orthogonal packing forms. The structural details of the
obtained 1D columnar packing structures are discussed in comparison with precedented examples
including 5,10-diphenylporphyrin Cu(II) and Ag(II) complexes, 5,10-diphenyl N-confused porphyrin
Ag(III) complex and 5,10-bis(pentafluorophenyl)corrole.
KEYWORDS: porphyrin, metal complex, X-ray diffraction analysis, packing structure, polymorph.
principle for columnar packing in the solid-state is
INTRODUCTION
essentially useful for applications in materials science.
Molecular assembly in the solid state plays a vital role
Herein, we show an interesting tendency of 5,10-diaryl-
for electronics applications such as OFET and OPV [1].
A variety of p-conjugated molecules have been studied to
exploit effective conducting properties through overlap
substituted porphyrins to stack in a 1D columnar fashion
in the single crystal.
of p-orbitals. Among them, porphyrins have been
regarded as a good motif because of their square-planar
RESULTS AND DISCUSSION
structure, effective p-conjugation, strong visible light
absorption, and rich metal coordination ability. By virtue
Synthesis of 5,10-diphenylporphyrin 1H has been
previously reported by several groups [6]. In our own
of these advantages, discotic columnar liquid crystalline
right, we found better reaction conditions for acid-
molecules based on porphyrin scaffolds have been
catalyzed condensation of 5,10-diphenyltripyrrane (3a)
[7] and 2,5-di(hydroxymethyl)pyrrole (4) (Scheme 1)
[8]. To a mixture of 3a and 4 in chloroform was added a
catalytic amount of BF3 ·OEt2, and the resulting mixture
developed to exhibit a promising conductive character
[2, 3]. In addition, it is well known that a 1D columnar
stacking structure in the single crystal state also offers an
effective conducting pathway with significant isotropic
was stirred for 1 h at room temperature, followed by
character (Fig. 1) [4]. Since the solid-state packing of
oxidation conducted with 5 equivalents of chloranil.After
the usual work-up, the residual solids were subjected
to separation by column chromatography. Notably, a
porphyrins is often susceptible to peripheral substituents
(i.e. b-alkyl and meso-aryl substituents) [5], a design
troublesome contamination with 5,15-diphenylporphyrin
or 5-phenylporphyrin was somehow suppressed, and
1H was obtained in 12% yield [9]. In a similar but
*Correspondance to: Takayuki Tanaka, email: taka@kuchem.
kyoto-u.ac.jp; Atsuhiro Osuka. email: osuka@kuchem.kyoto-u.
ac.jp; Tel: +81 75-753-4007. Fax: +81 75-753-3970.
Copyright © 2017 World Scientific Publishing Company

2
T. TANAKA ET AL.
structure of 1H by ourselves, no polymorphs were
found, likely because this packing structure does not
include void spaces occupied by solvent molecules.
In the meantime, we have successfully grown single
crystals of 2H by slow-vapor diffusion of n-heptane into
a chlorobenzene solution of 2H. X-ray diffraction (XRD)
analysis revealed that two porphyrins are p–p stacked in
a complementary manner with an interplanar distance
of 3.395Å (Fig. 2). A set of two stacked porphyrins is
packed perpendicular to the neighboring set in a closest
(b-H)–(porphyrin p plane) distance of 2.639Å. Since
the unit cell included chlorobenzene molecules, other
solvent systems were examined. Although single crystals
were also obtained from a 1,2-dichlorobenzene/n-octane
system, the packing structure was almost the same (see
Supporting information).
Fig. 1. Schematic representations for packing structures of
porphyrins
slightly modified manner, a condensation reaction of
5,10-bis(pentafluorophenyl)tripyrrane (3b) [10] with
4 followed by oxidation with chloranil gave 5,10-
bis(pentafluorophenyl)porphyrin 2H in 17% yield. 2H
would be a useful building-block for the construction of
designed porphyrin arrays [11]. Metal complexes of 1H
and 2H were prepared according to the usual procedures
(see the experimental section). Thus, Ni(II) complexes
1Ni and 2Ni, and Zn(II) complexes 1Zn and 2Zn were
prepared.
In a recent report by Senge et al., the crystal structure
of 1H has been shown in detail [12]. In the solid-state
of 1H, porphyrins are stacked in a so-called herringbone
manner with an interplanar distance of 3.681Å. The two
phenyl groups are tilted against the porphyrin plane by
55–62°. As long as we re-investigated the solid-state
In the course of our study, we found different types
of single crystals of 2Ni depending on the solvent
system used to grow them. A single crystal grown from
a mixture of toluene and n-heptane looks like a rhombic
plate. The XRD analysis of the crystal showed a dimeric
stacking form similarly to the case of 2H (Fig. 3a). On
the other hand, thin fiber-like crystals were obtained
by slow vapor diffusion of n-octane into a solution of
2Ni in 1,2-dichlorobenzene. Interestingly, the XRD
analysis of the crystal revealed a 1D columnar stacking
structure (Fig. 3b), in which each porphyrin unit is
stacked in a complementary manner to avoid the steric
congestion between the pentafluorophenyl groups at the
meso-positions. The interplanar distances (d1 and d2)
are calculated to be 3.399 and 3.531Å and the Ni–Ni
distances are 4.418 and 3.970Å, respectively. From these
Scheme 1. Synthesis of 5,10-diarylporphyrins
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1D COLUMNAR STACKING STRUCTURES IN THE SINGLE CRYSTALS OF 5,10-DIARYLPORPHYRIN METAL COMPLEXES
3
of n-heptane and n-octane into the 1,2-dichlorobenzene
solutions, respectively. The XRD analyses revealed
1D columnar stacking structures in both cases. 1Zn
crystallizes in the triclinic space group with one molecule
in the asymmetric unit (Fig. 4a). The interplanar distances
are calculated to be 3.270 and 3.324Å. On the other hand,
2Zn crystallizes in the monoclinic space group with two
independent molecules in the asymmetric unit. Although
the structural details about the packing structure of
2Zn become complicated, the interplanar distances are
calculated to be 3.090, 3.195, 3.371, and 3.411Å, being
in the range of typical p–p stacking distance (Fig. 4b).
The horizontal offset distances are calculated; 1.858 and
1.808Å for 1Zn, and 4.274, 2.367, 1.525 and 2.043Å
for 2Zn. Relatively larger offset distances in 2Zn are
notable, which is partly ascribed to the disordering of the
solvate molecules in the crystal lattice.
Regarding the trend to form 1D columnar packing
structures in the single crystals of 5,10-disubstituted por-
phyrins, let us consider the generality of this phenomenon.
Fig. 2. Solid-state packing structure of 2H. Single crystals
Very recently, Senge et al. reported a copper(II) complex
were grown from chlorobenzene/n-heptane. Solvent molecules
included in the crystal lattice were omitted for clarity
of 5,10-diphenylporphyrin (1Cu) which showed columnar
packing similar to the case of 1Zn [12]. 5,10-Diphenyl-
substituted silver(II) porphyrin 1Ag and silver(III)
N-confused porphyrin 5Ag both were reported to display
1D columnar stacking structures in the single crystal state
[13]. In another case, 5,10-bis(pentafluorophenyl)corrole
(6H) has been recently reported to form a 1D columnar
packing structure, and this is likely the only example
of freebase 5,10-disubstituted porphyrinoid that forms
columnar stacking in the single crystal [14]. In contrast,
values, the horizontal offset distances are calculated to be
2.822 and 1.815Å. Despite our continuous attempts, the
crystal structure of 1Ni was not obtained, mainly due to
the poor solubility.
Fiber-like crystals of 1Zn and 2Zn suitable for
XRD analysis were obtained by slow-vapor diffusion
Fig. 3. Solid-state packing structures of 2Ni in different packing modes. The single crystals were grown from (a) toluene/n-heptane
and (b) 1,2-dichlorobenzene/n-octane. The solvent molecules included in the crystal lattice were omitted for clarity
Copyright © 2017 World Scientific Publishing Company
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4
T. TANAKA ET AL.
Fig. 4. X-ray crystal structures of (a) 1Zn and (b) 2Zn. Single crystals were grown from (a) 1,2-dichlorobenzene/n-heptane and
(b) 1,2-dichlorobenzene/n-octane. The solvent molecules included in the crystal lattice were omitted for clarity
Table 1. Summary of structural details for columnar stacked porphyrinoids
Compd.
1Zn
Interplane distance [Å]
3.324, 3.270
Horizontal offset distance [Å]a
1.808, 1.858
MPD [Å]b
0.028
1Cu[12]
1Ag[13]
2Zn
3.292, 3.285
1.698, 1.711
0.018
3.322, 3.299
1.641, 1.686
0.020
3.090, 3.195, 3.371, 3.411
3.531, 3.399
4.274, 2.367, 1.525, 2.043
1.815, 2.822
0.055, 0.047
0.126
2Ni
5Ag[13]
6H[14]
3.307, 3.319
1.642, 1.699
0.026
3.400, 3.431, 3.304, 3.368
2.550, 2.117, 2.481, 2.148
0.046, 0.053
a The horizontal offset distances are calculated by [(metal-metal distance)2–(interplane distance)2]1/2. For
a freebase, an empty metal center was defined as the gravity center of four nitrogens. b The mean-plane
was defined by core 24 atoms in the case of porphyrins and by core 23 atoms in the case of corrole.
cobalt(III) and gallium(III) complexes of 6H did not form
1D stacking structures due to the axially metal-coordinated
pyridines [15].
All the columnar stacking structures discussed in
this paper are compared in Table 1. For 1Zn, 1Cu, 1Ag
and 5Ag, the interplanar distances fall within the range
of 3.27–3.32Å, and the horizontal offset distances are
shorter (1.64–1.86Å). In these molecules, smaller mean
plane deviation (MPD) values (less than 0.03Å) are
favorable for the formation of the p-stacked structures.
On the other hand, p–p overlapping was somewhat
hampered for a less planar porphyrin such as 2Ni (MPD:
0.126Å) that displays larger interplanar and horizontal
offset distances. 2Zn and 6H displayed relatively large
interplanar and horizontal offset distances despite their
relatively smaller MPD values. Both single crystals
contained two independent molecules in their assymetric
units, making the unit cell larger and the void space
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1D COLUMNAR STACKING STRUCTURES IN THE SINGLE CRYSTALS OF 5,10-DIARYLPORPHYRIN METAL COMPLEXES
5
Fig. 5. Examples of 5,10-disubstituted porphyrinoids reported previously
expanded. As a result, the columnar packing structure
became less suitable to form rigid packing. Thus, the
choice of solvent molecules that could be included
between columnars is crucial, so that polymorphic
crystals can be easily expected as seen in 2Ni. This work
may invoke further investigation on porphyrinic crystal
engineering in light of numerous intriguing applications
such as guest encapsulation, spin array and isotropic
conductivity [16].
and refined with the full-matrix least square technique
(SHELXL-97).
5,10-Diphenylporphyrin (1H)
5,10-Diphenyltripyrrane (3a) (1.5 g, 4.0 mmol) was
dissolved in degassed chloroform (500 mL), to which
a solution of 2,5-dihydroxymethylpyrrole (4) (505 mg,
4.0 mmol) in methanol was added. After the mixture
was stirred for 10 min, borontrifluoride diethyletherate
(0.10 mL, 20 mol%) was added and the solution was
stirred for 1 h at room temperature in the dark. Chloranil
(4.9 g, 5 equiv) was added to the reaction mixture and the
mixture was further stirred for 40 min. Then the solution
was passed through an alumina column and a silica-gel
column. The solution was evaporated to remove the
solvent and the residue was purified by recrystallization
from dichloromethane/methanol to afford 1H (221 mg,
0.48 mmol, 12%). The spectroscopic data have been
reported previously [6].
EXPERIMENTAL
General
Commercially available solvents and reagents were
used without further purification unless otherwise
noted. Spectroscopic grade solvents were used for
all the spectroscopic studies. Silica gel column chro-
matography was performed on a Wakogel C-300.
Alumina column chromatography was performed on a
Sumitomo g-Alumina KCG-1525W (Blockmann grade
II). Thin-layer chromatography (TLC) was carried out on
aluminum sheets coated with silica gel 60 F254 (Merck
5554). UV-Vis absorption spectra were recorded on a
Shimadzu UV-3600 spectrometer. Fluorescence spectra
were recorded on a Shimadzu RF-5300PC spectrometer.
Absolute fluorescence quantum yields were determined on
5,10-Bis(2,3,4,5,6-pentafluorophenyl)porphyrin (2H)
5,10-Bis(2,3,4,5,6-pentafluorophenyl)tripyrrane (3b)
(2.5 g, 4.5 mmol) was dissolved in degassed dichlo-
romethane (2.0 L), to which a solution of 2,5-dihy-
droxymethylpyrrole (4) (570 mg, 4.5 mmol) in methanol
was added. After the mixture was stirred for several
minutes, p-toluene sulfonic acid monohydrate (120 mg,
16 mol%) was added and the solution was stirred for
16 h at room temperature in the dark. Chloranil (3.3 g,
3.1 equiv) was added to the reaction mixture and the
mixture was further stirred for 30 min. Then the solution
was passed through an alumina column and a silica-gel
column. The solution was evaporated to remove the
solvent and the residue was purified by recrystallization
from dichloromethane/methanol to afford 2H (480 mg,
0.75 mmol, 17%).
1
a HAMAMATSU C9920-02S. H and 19F NMR spectra
were recorded on a JEOL ECA-600 spectrometer (opera-
1
ting at 600.17 MHz for H and 564.73 MHz for 19F)
using the residual solvent as the internal reference for 1H
(d = 7.26 ppm in CDCl3) and hexafluorobenzene as an
external reference for 19F (d = 162.9 ppm). High-resolution
atmospheric-pressure-chemical-ionization time-of-flight
mass-spectroscopy (HR-APCI-TOF-MS) was performed
on a BRUKER micrOTOF model using positive mode.
Crystal data
2H; 1H NMR (600.17 MHz; CDCl3): d, ppm 10.36 (s,
2H, por-meso), 9.50 (s, 2H, por-b), 9.46 (d, J = 4.8 Hz,
2H, por-b), 8.97 (d, J = 4.8 Hz, 2H, por-b), 8.95 (s, 2H,
por-b) and -3.44 (s, 2H, NH); 19F NMR (564.73 MHz;
CDCl3) d (ppm): -137.86 (d, J = 17.5 Hz, 4F, o-F),
-152.15 (t, J = 21.9 Hz, 2F, p-F) and -161.79 (d, J =
Single-crystal X-ray diffraction analysis data for
2H, 2Ni, 1Zn, and 2Zn were collected at -180°C with
a Rigaku XtaLAB P200 using graphite monochromated
Cu-Ka radiation (l = 1.54187 Å) (Table 2). The struc-
tures were solved by direct methods (SHELXS-97)
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T. TANAKA ET AL.
Table 2. Crystal data structure refinements for 2H, 2Ni, 1 Zn and 2Zn
Compound
2H
2Ni
2Ni
1Zn
2Zn
2(C32H12F10N4)·
C6H4Cl
2(C32H10F10N4Ni)·
C7H8
C32H10F10N4Ni·
1.5(C6H14Cl2)
C32H20N4Zn·
C6H4Cl2
2(C32H10F10N4Zn)·
C6H4Cl2·0.5(C6Cl2)
Empirical formula
MW
1397.46
93 (2)
1490.39
93 (2)
919.64
93 (2)
672.9
93 (2)
3260.26
93 (2)
T [K]
Crystal system
Space group
a [Å]
Monoclinic
P 21/a (No. 14)
12.258 (4)
14.505 (5)
16.184 (5)
90
Orthorhombic
P can (No. 60)
12.5641 (12)
14.3019 (13)
31.686 (3)
90
Monoclinic
P 21/c (No. 14)
7.440 (2)
19.583 (4)
24.048 (6)
90
Triclinic
Monoclinic
C 2/m (No. 15)
19.530 (5)
25.401 (6)
13.044 (3)
90
P -1 (No. 2)
6.6099 (18)
12.212 (5)
18.562 (5)
103.027 (1)
95.391 (3)
96.693 (19)
1438.6 (8)
2
b [Å]
c [Å]
a [deg]
b [deg]
g [deg]
Volume [Å3]
Z
94.7115 (6)
90
90
97.203 (6)
90
97.034 (9)
90
90
2870.1 (16)
2
5693.7 (9)
4
3476.1 (15)
4
3211 (3)
4
Density [Mg/m3]
1.617
1.739
1.757
1.682
1.686
Crystal size [mm3]
Completeness
0.07 × 0.05 × 0.01 0.16 × 0.09 × 0.03 0.06 × 0.03 × 0.02 0.56 × 0.06 × 0.02 0.03 × 0.02 × 0.01
0.991
0.986
0.99
0.96
0.99
Reflections collected/
unique
18699/5065
20060/5000
23105/6125
16950/4403
19786/5269
Goodness-of-fit
R1 [I > 2s (I)]
wR2 [I > 2s (I)]
R1 (all data)
1.016
0.0688
1.053
0.0286
1.069
0.0461
1.015
0.0307
1.008
0.0645
0.1814
0.0786
0.1106
0.0812
0.182
0.1162
0.0341
0.0727
0.0338
0.0786
wR2 (all data)
CCDC
0.2057
0.0806
0.1221
0.0827
0.1968
1582878
C6H5Cl/heptane
1582880
toluene/heptane
1582879
C6H4Cl2/octane
1582877
C6H4Cl2/heptane
1582881
C6H4Cl2/octane
Solvent systems
R1 = Σ(||F0| – |Fc||)/Σ|F0|, wR2 = Σw(|F0|2 – |Fc|2)2/Σw(|F0|2)2]1/2.
17.5 Hz, 4F, m-F); HR-APCI-TOF-MS: m/z 642.0891,
calcd. for C32H12F10N4 642.0897 [M]+. UV-vis (CH2Cl2):
gel, and evaporated to remove the solvent. Purification
was carried out by silica gel column chromatography and
recrystallization. The spectroscopic data of 1Zn have
been reported previously (Fig. 5) [6a].
l
max, nm (e [M-1cm-1]) = 404 (184000), 498 (12200)
and 571 (4200); fluorescence (CH2Cl2, lex = 571 nm):
max, nm = 624 and 688, FF = 0.030.
1
l
2Zn; H NMR (600.17 MHz; acetone-d6): d, ppm
10.55 (s, 2H, por-meso), 9.67 (s, 2H, por-b), 9.63 (d, J =
4.6 Hz, 2H, por-b), 9.24 (d, J = 4.6 Hz, 2H, por-b), and
9.22 (s, 2H, por-b); 19F NMR (564.73 MHz; acetone-d6):
d ppm -139.83 (d, J = 17.7 Hz, 4F, o-F), -156.80 (t,
J = 17.5 Hz, 2F, p-F) and -165.36 (t, J = 17.5 Hz, 4F,
m-F); HR-APCI-TOF-MS: m/z 704.0029, calcd. for
C32H10F10N464Zn704.0032[M]+.UV-vis(CH2Cl2):lmax,nm
(e [M-1cm-1]) = 404 (303000), 534 (7900) and 568 (3000);
fluorescence (CH2Cl2, lex = 534 nm): lmax, nm 572 and
621, FF = 0.015.
General procedure for the synthesis of zinc(II)
porphyrins
A saturated solution of Zn(OAc)2 in methanol was
added to a solution of 1H or 2H in chloroform and the
resulting mixture was stirred for 2–3 h at 40–50°C. The
reaction mixture was quenched with water and extracted
with chloroform. The organic layer was dried with
anhydrous Na2SO4, passed through a short plug of silica
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1D COLUMNAR STACKING STRUCTURES IN THE SINGLE CRYSTALS OF 5,10-DIARYLPORPHYRIN METAL COMPLEXES
7
General procedure for the synthesis of nickel(II)
porphyrins
REFERENCES
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mixture was stirred overnight under reflux. The reaction
mixture was quenched with water and extracted with
dichloromethane. The organic layer was dried with
anhydrous Na2SO4, passed through a short plug of silica
gel, and evaporated to remove the solvent. Purification
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2Ni; 1H NMR (600.17 MHz; CDCl3): d, ppm 10.02 (s,
2H, por-meso), 9.31 (s, 2H, por-b), 9.30 (d, J = 4.6 Hz,
2H, cor-b), 8.85 (d, J = 4.6 Hz, 2H, por-b), and 8.82
(s, 2H, por-b); 19F NMR (564.73 MHz; CDCl3): d, ppm
-137.86 (d, J = 17.5 Hz, 4F, o-F), -153.42 (t, J = 21.9 Hz,
2F, p-F) and –162.92 (t, J = 17.5 Hz, 4F, m-F); HR-APCI-
TOF-MS: m/z 698.0099, calcd. for C32H10F10N458Ni
698.0094 [M]+. UV-vis (CH2Cl2): lmax, nm (e [M-1cm-1]):
394 (231000), 515 (13700) and 548 (15500).
CONCLUSION
In summary, we revealed that 5,10-diarylporphyrin
Zn(II) and Ni(II) complexes showed 1D columnar stacking
structures in the single crystal state, while such a packing
mode has never been found in free-base porphyrins.
Ni(II) 5,10-diphenylporphyrin 2Ni showed polymorphs
depending on the solvents used for recrystallization. Taking
the 1D columnar packing of 5Ag and 6H into considera-
tion together, we conclude that 5,10-diarylporphyrinoids
are promising candidates to form a 1D columnar packing
structure in the single-crystal state.
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Acknowledgements
This work was supported by JSPS KAKENHI Grant
Numbers (JP25220802, JP26810021, JP15K05419,
JP17H03042, and JP16H00909).
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Figures of NMR spectra, mass spectra, and crystallo-
graphic data 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
numbers CCDC-1582878 (2H), 1582879-1582880 (2Ni),
1582877 (1Zn) and 1582881 (2Zn). Copies can be obtained
on request, free of charge, via http://www.ccdc.cam.ac.uk/
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