Synthesis and photophysical properties of doubly β-to-β bridged cyclic ZnII porphyrin arrays

Article abstract of DOI:10.1002/asia.201300035

A series of doubly β-to-β bridged cyclic Zn^II porphyrin arrays were prepared by a stepwise Suzuki-Miyaura coupling reaction of borylated Zn^II porphyrin with different bridge groups. The coupling of the building block of β,β′-diboryl Zn^II porphyrin with different bridges provided the doubly β-to-β carbazole-bridged Zn^II porphyrin array, the fluorene-bridged Zn^II porphyrin array, the fluorenone-bridged Zn^II porphyrin array, and the three-carbazole-bridged Zn^II porphyrin ring. The structural assignment of was confirmed by the X-ray diffraction analysis, which revealed a highly symmetrical and remarkably bent syn-form structure. The incorporation of bridge units with different electronic effects results in different photophysical properties of the cyclic Zn^II porphyrin arrays. Comprehensive photophysical studies demonstrate that the electron-withdrawing bridge fluorenone has the largest electronic interaction with the Zn ^II porphyrin unit among the series, thus resulting in the highest two-photon absorption cross-section values (σ⁽²⁾) of 6570±60 GM for. The present work provides a new strategy for developing porphyrin-based optical materials. Do you cross the bridge or do you fade away: Doubly β-to-β bridged cyclic Zn^II porphyrin arrays with carbazole, fluorene, and fluorenone as bridges were constructed. The incorporation of bridge units with different electronic effects results in different photophysical properties of the cyclic Zn^II porphyrin arrays.

Full text of DOI:10.1002/asia.201300035

FULL PAPER
DOI: 10.1002/asia.201300035
Synthesis and Photophysical Properties of Doubly b-to-b Bridged Cyclic ZnII
Porphyrin Arrays
Qingshan Hao,[a] Yi Zeng,[a] Tianjun Yu,[a] Jinping Chen,*[a] Guoqiang Yang,*[b] and
Yi Li*[a]
Abstract:
A
series of doubly b-to-
ring 8. The structural assignment of 3
was confirmed by the X-ray diffraction
analysis, which revealed a highly sym-
metrical and remarkably bent syn-form
structure. The incorporation of bridge
units with different electronic effects
results in different photophysical prop-
erties of the cyclic ZnII porphyrin
arrays. Comprehensive photophysical
studies demonstrate that the electron-
withdrawing bridge fluorenone has the
largest electronic interaction with the
ZnII porphyrin unit among the series,
thus resulting in the highest two-
photon absorption cross-section values
(s(2)) of 6570Æ60 GM for 7. The pres-
ent work provides a new strategy for
developing porphyrin-based optical
materials.
b bridged cyclic ZnII porphyrin arrays
were prepared by a stepwise Suzuki–
Miyaura coupling reaction of borylated
ZnII porphyrin with different bridge
groups. The coupling of the building
block of b,b’-diboryl ZnII porphyrin
1 with different bridges provided the
doubly b-to-b carbazole-bridged ZnII
porphyrin array 3, the fluorene-bridged
ZnII porphyrin array 5, the fluorenone-
bridged ZnII porphyrin array 7, and the
three-carbazole-bridged ZnII porphyrin
Keywords: conjugation
·
cross-
coupling · macrocycles · porphyri-
noids · two-photon absorption
Introduction
unique electronic properties that differ from their linear an-
alogues.
Porphyrin, as a versatile molecule, plays an important role
in both natural photosynthetic systems and in the chemistry
world. The wide use of porphyrin-based chromophores in
fields such as host–guest chemistry, material chemistry, and
molecular photochemistry, has evoked extensive interest in
the synthesis and functionalization of porphyrinic molecules.
Recently, covalently linked porphyrin oligomers have drawn
much attention because of their potential applications in
molecular electronic devices,[1] dye-sensitized solar cells
(DSSCs),[2] and nonlinear optical materials.[3] Among these
oligomers, cyclic porphyrin arrays constructed by means of
covalent bonds are particular attractive because of their
Progress in the synthesis of porphyrin arrays relies on the
development of new coupling reactions. The synthesis of
meso-to-meso linked ZnII porphyrin arrays by AgPF6-pro-
moted oxidation of 5,15-diaryl substituted ZnII porphyrin
launched a new area of synthetic porphyrin chemistry, yield-
ing large linear, cyclic, and sheet ZnII porphyrin arrays.[4] Up
to now, most covalently bonded cyclic porphyrin arrays re-
ported were constructed by using the meso-to-meso bridging
method,[5] and only a few studies have dealt with the synthe-
sis of b-to-b bridged cyclic porphyrin arrays. As another ef-
fective synthetic protocol, the introduction of suitable
groups at b-positions also has a significant effect on the elec-
tronic properties of porphyrins.[6] Recently, Osuka and Shi-
nokubo et al. developed an iridium-catalyzed method for
the direct borylation of porphyrin at the b-position with
high regioselectivity,[7] which makes it possible to add fur-
ther functionalization at this position.[6b,8] By using the build-
ing block of b-borylated porphyrin, the authors reported the
synthesis of the b-to-b bridged cyclic porphyrin arrays with
[a] Q. Hao, Dr. Y. Zeng, Dr. T. Yu, Dr. J. Chen, Prof. Dr. Y. Li
Key Laboratory of Photochemical Conversion and Optoelectronic
Materials
Technical Institute of Physics and Chemistry
Chinese Academy of Sciences
Beijing, 100190 (P. R. China)
Fax : (+86)10-8254-3518
E-mail: yili@mail.ipc.ac.cn
1,3-butadiyne,[9]
2,6-pyridylene,[10]
and
2,5-thienylene
bridges,[11] and all the arrays exhibit unique photophysical
properties. The double-bridging strategy endows the porphy-
rin arrays with stiff conformations, which allows effective p-
delocalization and thus the formation of large conjugated
networks. The obtained results suggest that the structure of
the bridges at the b-position greatly affects the photophysi-
cal properties of cyclic porphyrin arrays.
chenjp@mail.ipc.ac.cn
[b] Prof. Dr. G. Yang
Beijing National Laboratory for Molecular Sciences (BNLMS)
Key laboratory of Photochemistry, Institute of Chemistry
Chinese Academy of Sciences
Beijing, 100190 (P. R. China)
Fax : (+86)10-8261-7315
E-mail: gqyang@iccas.ac.cn
To further clarify the bridge effect in cyclic porphyrin
arrays, we report herein the synthesis of a series of b-to-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201300035.
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Jinping Chen, Guoqiang Yang, Yi Li et al.
b bridged cyclic ZnII porphyrin arrays with carbazole, fluo-
rene, and fluorenone moieties as bridges. These bridges pos-
sess different electronic effects, that is, electron-donating,
electroneutral, and electron-withdrawing ones for carbazole,
fluorene, and fluorenone, respectively, although they have
similar geometrical structures. The studies on the ZnII por-
phyrin arrays with different bridges will disclose the rela-
tionship between the molecular structures and the photo-
physical properties, which will enable the design of porphy-
rin-based materials.
plished by recrystallization from CH2Cl2/MeOH (8:1), which
is more convenient than the separation of borylated free-
base porphyrin by recycling preparative gel permeation
chromatography–high performance liquid chromatography
(GPC–HPLC).[7,12] Then the Suzuki–Miyuara coupling reac-
tion of 1 (1 equiv) with 3,6-dibromocarbazole (5 equiv)[13]
was carried out under conditions of [Pd2ACTHNUTRGNEU(NG dba)3] (0.03 equiv),
PPh3 (0.12 equiv), Cs2CO3 (2.0 equiv), and CsF (2.0 equiv)
in a mixture of toluene and DMF (2:1) at 908C to afford
b,b’-dicarbazole ZnII porphyrin 2 in 76% yield. In the same
way, the double coupling of 1 with 2 furnished carbazole-
bridged ZnII porphyrin array 3 in 41% yield. The lower
yield of cyclization may be caused by the deborylation of
Results and Discussion
1
1 and the formation of linear analogues. The H NMR spec-
Synthesis
trum of 3 in CDCl3 at room temperature is simple, exhibit-
ing one singlet at 10.33 ppm for the meso-protons (Hm) and
two singlets at 9.00 and 8.94 ppm for the b-protons (Hb),
thereby reflecting its highly symmetric structure. The parent
ion peak of 3 was observed at m/z 2254.6 (calcd for
Carbazole-bridged ZnII porphyrin array 3: The procedure
for the synthesis of carbazole-bridged ZnII porphyrin array 3
is shown in Scheme 1. Borylation of 5,10,15-tris(3,5-di-tert-
C
152H162N10Zn2: 2258.2 [M]+) in its MALDI-TOF mass spec-
trum. The final structural confirmation was obtained by
single-crystal X-ray diffraction analysis (see below).
Fluorene-bridged ZnII porphyrin array 5 and fluorenone-
bridged ZnII porphyrin array 7: The successful preparation
of carbazole-bridged ZnII porphyrin array 3 suggested the
possibility of synthesizing cyclic ZnII porphyrin arrays with
other bridges. We then examined the Suzuki–Miyaura cou-
pling of 1 with 2,6-dibromofluorene and 2,6-dibromofluore-
none,[14] which have similar molecular structures but differ-
ent electronegativities compared with 2,6-dibromocarbazole.
With the same procedure as for the preparation of 3, treat-
ment of 1 with 2,6-dibromofluorene or 2,6-dibromofluore-
none in the presence of [Pd2ACHTNUTRGENNUG(dba)3] as catalyst furnished
b,b’-difluorene ZnII porphyrin 4 or b,b’-difluorenone ZnII
porphyrin 6 in yields of 80% and 48%, respectively. The
different coupling yields may be attributed to the different
electronegativities of the bridges. The double coupling reac-
tion of 1 with 4 or 6 afforded the desired fluorene-bridged
ZnII porphyrin array 5 and fluorenone-bridged ZnII porphy-
rin array 7 in 38% and 22% yields, respectively (Scheme 2).
1
Both 5 and 7 exhibit simple H NMR spectra with a singlet
(Hm) at 10.27 ppm for 5 and 9.87 ppm for 7, which are indi-
cative of symmetrical cyclic structures. The parent ion peaks
were observed at m/z 2477.6 for 5 (calcd for C170H196N8Zn2:
2480.4 [M]+) and at m/z 2226.2 for
C
7
(calcd for
150H152N8O2Zn2: 2228.1 [M]+), respectively, in the MALDI-
TOF mass spectra.
Three carbazole-bridged ZnII porphyrin ring 8: To better
understand the role of bridges in the cyclic ZnII porphyrin
arrays, we continued with the synthesis of the ZnII porphyrin
ring 8 composed of one ZnII porphyrin unit and three carba-
zole groups. This array was obtained in 45% yield by treat-
ment of 2 (1 equiv) and 3,6-diborylcarbazole (1 equiv) in the
Scheme 1. Synthesis of the carbazole-bridged ZnII porphyrin array 3.
butylphenyl) ZnII porphyrin (1 equiv) with bis(pinacolato)di-
borane (10 equiv) in the presence of a catalytic amount of
[Ir
G
presence of [Pd2ACTHUNGTERNNU(G dba)3] as catalyst in a mixture of toluene
yl (dtbpy, 0.10 equiv) in 1,4-dioxane provided a known com-
pound of b,b’-diboryl ZnII porphyrin 1[6b] in 82% yield. The
purification of diborylated ZnII porphyrin is easily accom-
and DMF (2:1) at 908C (Scheme 3). Because the synthesis
of 3,6-diborylfluorene and 3,6-diborylfluorenone failed
under the same conditions, we did not obtain similar struc-
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The N-Zn-N angles in the ZnII
porphyrin unit are 165.3–167.58,
which means that the zinc atom
is slightly out of the plane of
porphyrin. The center-to-center
distance between the zinc
atoms is about 13.35 ꢁ. The
carbazole bridges are connected
to the neighboring pyrroles
with dihedral angles of 96.98,
64.18, 129.28, and 86.58, thus im-
plying a limited delocalization
of the porphyrin
p circuits
through the bridges. The bond
lengths between the porphyrin
and the neighboring carbazole
(1.47–1.49 ꢁ) are close to those
À
of normal C C single bonds
(1.54 ꢁ), further suggesting the
poor conjugation between the
porphyrin core and the carba-
zole bridge. The crystal struc-
ture validates the analysis of
Scheme 2. Synthesis of the fluorene-bridged ZnII porphyrin array 5 and the fluorenone-bridged ZnII porphyrin
array 7. Reagents and conditions: b,b’-diboryl ZnII porphyrin 1, [Pd
2ACHTUNGTRNEUNG(dba)3], PPh3, Cs2CO3, CsF, toluene/DMF,
1
the H NMR spectrum.
reflux.
Scheme 3. Synthesis of carbazole-bridged ZnII porphyrin ring 8.
tures of three fluorene- or fluorenone-bridged ZnII porphy-
rin rings. The structure of 8 was confirmed by 1H NMR
spectroscopy and MALDI-TOF mass spectrometry, with
a meso proton resonance at 10.68 ppm and a parent ion
peak at m/z 1515.6 (calcd for C104H103N7Zn: 1514.8 [M]+).
Figure 1. X-ray crystal structure of carbazole-bridged ZnII porphyrin
array 3. a) Top view and b) side view. The thermal ellipsoids are drawn at
the 50% probability level. For clarity, tert-butyl groups, solvent mole-
cules, and hydrogen atoms are omitted.
X-ray Diffraction Analysis
Single crystals of the carbazole-bridged ZnII porphyrin array
3 suitable for X-ray diffraction analysis were obtained by
slow diffusion of methanol vapor into a toluene solution of
3. The obtained structure is depicted in Figure 1. Clearly,
the carbazole-bridged ZnII porphyrin array 3 displays a re-
markably bent syn-form structure with a diporphyrin dihe-
dral angle of 93.48, and the two carbazole bridges exhibit
the same conformation with a dihedral angle of 136.28,
while the nitrogen atoms point to the outside of the cycle.
Photophysical Characterization of the ZnII Porphyrin
Arrays
The UV/Vis absorption and fluorescence spectra of the
cyclic ZnII porphyrin arrays 3, 5, and 7, and of the 5,10,15-
tris(3,5-di-tert-butylphenyl) ZnII porphyrin monomer in
CH2Cl2 are shown in Figure 2 and Figure 3, respectively. All
the cyclic ZnII porphyrin arrays exhibit the typical absorp-
tion characteristics of the ZnII porphyrin monomer with
3
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ZnII porphyrin arrays exhibit typical vibronic structures with
a slight bathochromic shift in comparison with the bands of
the ZnII porphyrin monomer, and the emission maxima
change in the same sequence as the maxima of the Soret
and Q bands. The Stokes shifts of the cyclic ZnII porphyrin
arrays are smaller than those of the corresponding acyclic
ones (2, 4, and 6), further demonstrating the restriction of
the geometric change of the cyclic arrays in the excited
state. The Stokes shift of the cyclic array 7 is slightly larger
than that of the ZnII porphyrin monomer, thus indicating an
effect of the electron-withdrawing bridge, possibly implying
the formation of a sort of D-p-A structure.[15] The fluores-
cence quantum yields for all the ZnII porphyrin arrays are
between 0.014 and 0.025.
Figure 2. UV/Vis absorption spectra of the ZnII porphyrin arrays 3, 5, and
7 in CH2Cl2.
Fluorescence lifetimes were determined for all the mole-
cules to obtain information about the excited states of the
ZnII porphyrin arrays. Figure S23 in the Supporting Informa-
tion shows the time-resolved fluorescence decay profiles of
the cyclic ZnII porphyrin arrays, the bridge-substituted acylic
monomers, and the 5,10,15-tris(3,5-di-tert-butylphenyl) ZnII
porphyrin monomer. The fluorescence lifetimes of the cyclic
ZnII porphyrin arrays and the bridge-substituted acylic mon-
omers are similar to that of the ZnII porphyrin monomer
except the fluorenone substituted ones, which indicates
a lack of the inter-porphyrin electronic communication
through the bridges. The slightly shortened lifetime of the
fluorenone-substituted ZnII porphyrin compounds can be ra-
tionalized by the substituent effect and a relatively larger
effect of the electron-withdrawing group, which is consistent
with the results of steady-state photophysical studies. The
photophysical data for the ZnII porphyrin arrays, the bridge-
substituted acylic monomers, and the ZnII porphyrin mono-
mer are collected in Table 1.
Figure 3. Emission spectra of the ZnII porphyrin arrays 3, 5, and 7 in
CH2Cl2 at lex =550 nm.
a strong absorption band at around 420 nm and a weak one
at about 550 nm assigned to the Soret (B) band and the Q
band, respectively. However, a slight bathochromic shift of
the Soret band along with an obvious broadening was ob-
served for the ZnII porphyrin
arrays compared with that of
Table 1. Spectral properties of ZnII porphyrin arrays and monomers in CH2Cl2.
the ZnII porphyrin monomer
(lmax =416 nm). The full width
at half maximum (fwhm) of the
Soret bands increases in the
Absorption
lmax [nm]
Emission
lmax [nm]
Stokes shift
[cmÀ1
Quantum
yield
Lifetime
[ns]
TPA(s(2)
)
N
]
[GM][a]
ZnII
416, 543
590, 638
1467
0.033
2.2
<100
porphyrin
order of
5
(930 cmÀ1)<3
2
3
4
5
6
7
8
432, 552
421, 549
429, 550
420, 547
433, 552
423, 552
423, 549
608, 651
595, 645
609, 649
595, 644
616, 655
602, 648
599, 647
1669
1408
1761
1475
1882
1505
1520
0.017
0.013
0.021
0.019
0.005
0.014
0.025
2.3
2.1
2.3
2.1
1.8
1.8
1.9
760Æ20
(1469 cmÀ1)<7
(1651 cmÀ1),
5330Æ60
650Æ20
which is indicative of increasing
electronic interactions between
the porphyrin segments and the
bridges. The Soret and Q bands
5820Æ50
1640Æ20
6570Æ60
2620Æ20
of the bridge-substituted acylic
[a] Measured in toluene. GM, Goeppert–Mayer unit.
monomers 2, 4, and 6 exhibit
a larger red shift than those of
the corresponding cyclic ZnII porphyrin arrays (Figures S21
and S22 in the Supporting Information), thus indicating that
the conjugation between the bridge and the ZnII porphyrin
unit in the cyclic ZnII porphyrin arrays is restricted by the
constrained conformation. The absorption spectra of 3, 5,
and 7 are similar to that of the previously reported b,b’-
doubly 2,6-pyridylene-bridged porphyrin dimer,[10] thus sug-
gesting a lack of intramolecular electronic interaction be-
tween porphyrin units. The fluorescence spectra of all the
The two-photon absorption cross-section values (s(2))
were measured by using an open-aperture Z-scan method.
An 800 nm laser was chosen as the excitation light source to
completely eliminate the contribution from one-photon ab-
sorption. The open aperture Z-scan traces of the doubly b-
to-b bridged ZnII porphyrin arrays and the acylic monomers
are shown in Figure 4 and Figure S24 (Supporting Informa-
tion), respectively, and the obtained TPA cross-section data
are given in Table 1. All the cyclic ZnII porphyrin arrays
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Jinping Chen, Guoqiang Yang, Yi Li et al.
absorption and emission spectra
(Figure S19 and S20 in the Sup-
porting Information). We con-
clude that the multidimension-
ality of the cyclic structure of
the molecule plays the key role
for the enhancement of the
TPA cross-section of 8. The
TPA cross-section value of 8 is
about half the value of ZnII por-
phyrin array 3, which further
strengthens the notion of a con-
tribution of the multidimen-
sional cyclic structure to the
TPA cross-section.
Conclusions
In summary, we have accom-
plished the synthesis of a series
of doubly b-to-b bridged cyclic
ZnII porphyrin arrays by a step-
wise Suzuki–Miyaura coupling
reaction of borylated ZnII por-
phyrin with carbazole, fluorene,
Figure 4. Open aperture Z-scan traces of doubly b-to-b bridged ZnII porphyrin arrays. The solid lines are the
best fitted curves of the experimental data.
show a substantial increase in the TPA cross-section values
compared with the acyclic ones. Although the cyclic ZnII
porphyrin arrays have only one more ZnII porphyrin unit
than the acyclic ones, the TPA cross-section values of the
cyclic arrays are six, eight, and three times higher than those
of the corresponding carbazole-, fluorene-, and fluorenone-
bridged acylic ones, respectively. Therefore, the increased
number of the ZnII porphyrin unit is not the only reason for
the increase in the TPA cross-section values of the cyclic
arrays. Previous reports have demonstrated that the dimen-
sionality of conjugated molecules plays a decisive role in the
TPA properties.[3c,16] This suggests that the multidimensional
p delocalization and the associated molecular hyperpolariza-
bility induced by the cyclization in the ZnII porphyrin arrays
also contribute significantly to the TPA cross-section. For
the cyclic arrays, the TPA cross-section value increases in
the order of 3<5<7, thus indicating an effect of the bridge
structures. The electron-withdrawing group has a larger
effect on the enhancement of the TPA cross-section than
the electron-donating and electroneutral ones, which may be
attributed to the existence of a sort of D-p-A structure in 7.
To further understand the role of molecular structure, we
measured the TPA cross-section value of the ZnII porphyrin
ring 8 under the same conditions. The TPA cross-section
value of 8 (2620Æ20 GM) is about three times higher than
that of 2 (760Æ20 GM). Usually, intramolecular p delocali-
zation increases the TPA cross-section. However, the in-
creased TPA cross-section value of 8 here cannot be as-
cribed to an enhanced p delocalization because the electron-
ic interaction between the porphyrin unit and the bridge
substituents in 2 is higher than that in 8 according to their
and fluorenone as bridge structures, respectively. The single-
crystal X-ray diffraction analysis of carbazole-bridged ZnII
porphyrin array 3 confirmed unambiguously the formation
of the final cyclic structure. Based on the UV/Vis absorption
and fluorescence spectra, the electronic communication be-
tween the bridge and the ZnII porphyrin units is insignifi-
cant. The photophysical properties of cyclic ZnII porphyrin
arrays can be modulated by altering the coupling bridges,
and the electron-withdrawing bridge results in more obvious
effects. The present work provides a new strategy for the de-
velopment of porphyrin-based optical materials.
Experimental Section
Materials
Reagents were purchased from Acros, Alfa Aesar, or Beijing Chemicals
and used without further purification unless otherwise noted. 1,4-dioxane
and dichloromethane (CH2Cl2) were dried with sodium and CaH2, re-
spectively, and distilled under a N2 atmosphere. All solvents used for
spectroscopic measurements were spectral grade.
Instrumentation
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were obtained on
a Bruker Avance P-400 spectrometer with tetramethylsilane as an inter-
nal standard. MALDI-TOF-MS spectra were measured on a Bruker
BIFLEX III spectrometer. Elemental analyses were carried out on
a Flash EA1112 elemental analyzer (Thermo Electron). Absorption and
emission spectra were obtained on a Shimadzu UV-1601PC spectrometer
and a Hitachi F-4500 spectrometer, respectively. Fluorescence quantum
yields were determined under excitation at 550 nm, using ZnII tetraphe-
nylporphyrin (Zn-TPP) as a standard. Fluorescence decay processes were
recorded with a single photon counting technique on an Edinburgh
FLS920 fluorescence lifetime system, and the equipment resolution is
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~0.1 ns. X-ray crystallography data were taken on a Rigaku R-axis Rapid
IP diffractometer with MoKa radiation (l=0.71073 ꢁ).
insoluble salts (eluent: CH2Cl2). Then, the solvent was removed under re-
duced pressure, and the residue was purified by recrystallization from
a mixture of methanol and dichloromethane to afford b,b’-diboryl ZnII
porphyrin 1 as a dark red solid (978 mg, 82%). 1H NMR (400 MHz,
CDCl3): d=11.45 (s, 1H, meso), 9.73 (s, 2H, pyrrole-b), 8.98 (s, 4H, pyr-
role-b), 8.07 (d, J=22.7 Hz, 6H, Ar-o-H), 7.78 (d, J=11.8 Hz, 3H, Ar-p-
H), 1.71 (s, 24H), 1.55 (s, 36H, tert-butyl), 1.50 ppm (s, 18H, tert-butyl).
TPA Measurements
The TPA measurements were performed using the open-aperture Z-scan
method with 180 fs pulses from an optical parametric amplifier (Coher-
ent) operating at a 1 kHz repetition rate using a Ti:sapphire regenerative
amplifier system (Coherent Legend Elite ultrafast amplifier laser
system). After passing through a f=20 cm lens, the laser beam was fo-
cused at the center of a 1 mm-quartz cell. As the position of the sample
cell was varied along the laser-beam direction (z-axis), the transmitted
laser light from the sample cell was then probed by using an OPHIR
laser measurement group (NOVA II, PD300-3W-V1) as used for refer-
ence monitoring.
General Procedure for the Synthesis by the Suzuki–Miyaura Coupling
Reaction
b,b’-Diboryl ZnII porphyrin 1 (119.1 mg, 0.10 mmol, 1.0 equiv), bromo-
substituted bridges (1–5 equiv), [Pd2ACTHNUTRGEN(UNG dba)3] (0.03 equiv), PPh3
(0.12 equiv), Cs2CO3 (2.0 equiv), and CsF (2.0 equiv) were added to
a Schlenk flask, which was purged with argon and then charged with
dried toluene and DMF (2:1, 6 mL). The resulting mixture was thorough-
ly degassed through three freeze–pump–thaw cycles, and then stirred at
908C for 24 h under argon. The reaction was quenched with water and
extracted with CH2Cl2, and the organic layer was dried over anhydrous
sodium sulfate. After removal of the solvent under reduced pressure, the
residue was purified by column chromatography on silica gel to afford
the desired products.
3,6-Dibromofluorenone and 3,6-Dibromo-9,9’-dipentylfluorene
These compounds were synthesized according to a reported procedure.[14]
1H NMR (400 MHz, CDCl3) for 3,6-dibromofluorenone: d=7.68 (d, J=
1.3 Hz, 2H), 7.55 (d, J=7.8 Hz, 2H), 7.50 ppm (dd, J=7.9, 1.6 Hz, 2H);
1H NMR (400 MHz, CDCl3) for 3,6-dibromo-9,9’-dipentylfluorene: d=
7.78 (d, J=1.8 Hz, 2H, fluorene), 7.43 (dd, J=8.0, 1.8 Hz, 2H, fluorene),
7.19 (d, J=8.0 Hz, 2H, fluorene), 1.96–1.85 (m, 4H), 1.13–0.93 (m, 8H),
0.71 (t, J=6.9 Hz, 6H), 0.65–0.46 ppm (m, 4H).
b,b’-Dicarbazole ZnII Porphyrin 2
It was prepared by the coupling reaction of 1 with 3,6-dibromo-9-ethyl-
carbazole (5.0 equiv) according to the general procedure and purified by
column chromatography on silica gel (CH2Cl2/petroleum ether 1:4) and
recrystallization from 20% methanol/CH2Cl2 to afford 2 as a red solid in
76% yiled. 1H NMR (400 MHz, CDCl3): d=10.83 (s, 1H, meso), 9.21 (s,
2H, pyrrole-b), 9.06 (q, J=4.7 Hz, 4H, pyrrole-b), 8.98 (s, 2H, carba-
zole), 8.56 (d, J=8.3 Hz, 2H, carbazole), 8.29 (d, J=1.8 Hz, 2H, carba-
zole), 8.21 (d, J=1.7 Hz, 4H, Ar-H), 8.13 (d, J=1.7 Hz, 2H, Ar-H), 7.83
(s, 2H, Ar-H), 7.80 (s, 1H, Ar-H), 7.74 (d, J=8.4 Hz, 2H, carbazole),
7.59 (dd, J=8.7, 1.9 Hz, 2H, carbazole), 7.32 (d, J=8.7 Hz, 2H, carba-
zole), 4.37 (d, J=7.3 Hz, 4H, ethyl), 1.60–1.49 (m, 54H, tert-butyl),
1.36 ppm (t, J=7.1 Hz, 6H, ethyl); MS (MALDI-TOF): m/z calcd for
C90H92Br2N6Zn: 1480.5 [M]+; found: 1483.1.
3,6-Dibromo-9-ethylcarbazole
Carbazole (3.6 g, 0.2 mmol, 1.0 equiv) and dimethylformamide (DMF)
(40 mL) were added to a three-necked flask (100 mL), and a solution of
N-bromosuccinimide (NBS) (7.6 g, 0.4 mmol, 2.0 equiv) in DMF (20 mL)
was added dropwise at 08C. The mixture was then stirred at ambient
temperature for 2 h. Subsequently, the reaction was quenched with
excess water (200 mL) to produce a white precipitate, which was filtrated
and recrystallized from ethanol to afford 3,6-dibromocarbazole as
a white solid (5.0 g, 72.0%, m.p. 214–2168C). Next, 3,6-dibromocarbazole
(1.6 g, 5 mmol), bromoethane (1.5 g, 7.5 mmol), DMSO (100 mL), and
NaOH solution (5 mL, 50%) were added to
a three-necked flask
(250 mL), and the mixture was stirred at ambient temperature for 4 h.
The reaction was quenched with water and extracted with Et2O, and the
organic layer was dried over anhydrous sodium sulfate. After removal of
the solvent under reduced pressure, the residue was purified by recrystal-
Carbazole-bridged ZnII Porphyrin Array 3
It was prepared by the coupling reaction of 1 with 2 (1.0 equiv) according
to the general procedure and purified by column chromatography on
silica gel (CH2Cl2/petroleum ether 1:5) and recrystallization from 20%
methanol/CH2Cl2 to afford 3 as a red solid in 41% yield. 1H NMR
(400 MHz, CDCl3): d=10.33 (s, 2H, meso), 9.00 (s, 8H, pyrrole-b), 8.94
(s, 4H, pyrrole-b), 8.86 (s, 4H, carbazole), 8.15 (d, J=15.8 Hz, 8H, Ar-
H), 8.04 (s, 4H, Ar-H), 7.97 (d, J=9.2 Hz, 4H, carbazole), 7.76 (s, 2H,
Ar-H), 7.71 (s, 4H, Ar-H), 7.66 (d, J=8.4 Hz, 4H, carbazole), 4.57 (m,
J=7.0 Hz, 4H, ethyl), 1.63 (t, J=7.1 Hz, 6H, ethyl), 1.52–1.40 ppm (m,
108H, tert-butyl); 13C NMR (100 MHz, CDCl3): d=150.65, 150.07,
149.35, 148.85, 148.68, 148.59, 148.56, 147.52, 142.10, 141.98, 140.37,
132.70, 132.22, 131.93, 129.78, 129.11, 128.43, 123.66, 123.48, 122.63,
121.90, 120.85, 120.61, 104.73, 35.18, 35.10, 31.92, 31.85, 14.21 ppm; MS
lization from ether/CH2Cl2 to produce
a white solid (1.7 g, 80%).
1H NMR (400 MHz, CDCl3): d=8.14 (s, 2H, carbazole), 7.56 (d, J=
6.8 Hz, 2H, carbazole), 7.27 (d, J=9.5 Hz, 2H, carbazole), 4.31 (q, J=
7.2 Hz, 2H), 1.40 ppm (s, 3H).
3,6-Dibory-9-ethylcarbazole
3,6-Dibromo-9-ethylcarbazole (353.0 mg, 1.0 mmol, 1.0 equiv) and [Pd-
ACHTUNGTRENNUNG(PPh3)2Cl2] (70.2 mg, 0.1 mmol, 0.1 equiv) were placed in a Schlenk flask,
which was purged with argon and then charged with pinacolborane
(1.45 mL, 10.0 mmol, 10.0 equiv), Et3N (1.49 mL), and dried 1,4-dioxane
(4 mL). The mixture was stirred at reflux for 3 h under argon. After re-
moval of the solvent under reduced pressure, the crude product was puri-
fied by column chromatography on silica gel (CH2Cl2/petroleum ether=
1:4) and recrystallized from a mixture of dichloromethane and petroleum
ether to give a white solid (158 mg, 36% yield). 1H NMR (400 MHz,
CDCl3): d=8.67 (s, 2H, carbazole), 7.91 (dd, J=8.2, 0.9 Hz, 2H, carba-
zole), 7.40 (d, J=8.2 Hz, 2H, carbazole), 4.38 (q, J=7.2 Hz, 2H), 1.45–
1.37 ppm (m, 27H).
(MALDI-TOF): m/z calcd for
C
152H162N10Zn2: 2254.6 [M]+; found
2258.2; elemental anal. calcd. (%) for C152H162N10Zn2: C 80.79, H 7.23, N
6.20; found: C 80.55, H 7.46, N 6.01.
b,b’-Difluorene ZnII Porphyrin 4
It was prepared by the coupling reaction of 1 with 3,6-dibromo-9,9-pen-
tylfluorene (5.0 equiv) according to the general procedure and purified
by column chromatography on silica gel (CH2Cl2/petroleum ether 1:6)
and recrystallization from 20% methanol/CH2Cl2 to afford 4 as a red
solid in 80% yield. 1H NMR (400 MHz, CDCl3): d=10.92 (s, 1H, meso),
9.25 (s, 2H, pyrrole-b), 9.06 (dd, J=11.9, 4.7 Hz, 4H, pyrrole-b), 8.66 (s,
2H,fluorene), 8.39 (d, J=7.7 Hz, 2H, fluorene), 8.21 (d, J=1.7 Hz, 4H,
Ar-o-H), 8.11 (d, J=1.7 Hz,2H, Ar-o-H), 8.04 (d, J=1.7 Hz, 2H, fluo-
rene), 7.82 (dt, J=13.8, 1.8 Hz, 3H, Ar-p-H), 7.68 (d, J=7.7 Hz, 2H, flu-
orene), 7.51 (dd, J=8.1, 1.8 Hz, 2H, fluorene), 7.32 (d, J=8.1 Hz, 1H,
fluorene), 2.06–1.98 (m, 8H), 1.59 (s, 36H, tert-butyl), 1.54 (s, 18H, tert-
butyl), 1.11 (ddd, J=19.0, 12.8, 5.8 Hz, 16H), 0.86 (s,8H), 0.76 ppm (t,
b,b’-Diboryl ZnII Porphyrin 1
5,10,15-tris(3,5-di-tert-butylphenyl) ZnII porphyrin (938.7 mg, 1.0 mmol,
1.0 equiv), bis(pinacolato)diboron (2539.4 mg, 10.0 mmol, 10.0 equiv),
4,4’-di-tertbutyl-2,2’-bipyridyl (26.8 mg, 0.1 mmol, 0.1 equiv), and [Ir-
ACHTUNGTRENNUNG(OMe)ACHTUNGTRENNUNG(cod)]2 (33.2 mg, 0.05 mmol, 0.05 equiv) were added to a Schlenk
flask, which was evacuated and purged with argon five times, and then
charged with dried 1,4-dioxane (13.0 mL). The resulting mixture was
stirred at reflux for 72 h under argon. After removal of the solvent under
reduced pressure, the residue was dissolved in CH2Cl2. The solution was
filtered through a short column of silica gel to remove the catalyst and
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Jinping Chen, Guoqiang Yang, Yi Li et al.
J=7.0 Hz, 12H); MS (MALDI-TOF): m/z calcd for C108H126Br2N4Zn:
1705.3 [M]+; found: 1703.8.
123.15, 122.39, 122.31, 121.85, 121.75, 120.93, 120.82, 108.77, 108.54,
107.77, 104.58, 38.57, 38.09, 35.21, 35.17, 31.94, 31.59, 29.86, 29.52, 14.42,
14.27, 14.11 ppm; MS (MALDI-TOF): m/z calcd for C104H103N7Zn:
1515.6 [M]+; found: 1514.8; elemental anal. calcd. (%) for C104H103N7Zn:
C 82.37, H 6.85, N 6.47; found: C 82.02, H 7.10, N 6.38.
Fluorene-bridged ZnII Porphyrin Array 5
It was prepared by the coupling reaction of 1 with 4 (1.0 equiv) according
to the general procedure and purified by column chromatography on
silica gel (CH2Cl2/petroleum ether 1:6) and recrystallization from 20%
methanol/CH2Cl2 to afford 5 as a red solid in 38% yield. 1H NMR
(400 MHz, CDCl3): d=10.27 (s, 2H, meso), 8.96 (dd, J=11.6, 5.4 Hz,
12H, pyrrole-b), 8.47 (s, 4H, fluorene), 8.17–7.92 (m, 12H, Ar-H), 7.80
(d, J=8.6 Hz, 4H, fluorene), 7.74 (d, J=6.6 Hz, 6H, Ar-H), 7.66 (d, J=
7.8 Hz, 4H, fluorene), 2.21 (d, J=12.3 Hz, 4H, pentyl), 2.04 (d, J=
6.4 Hz, 4H, pentyl), 1.52–1.40 (m, 108H, tert-butyl), 1.27–1.17 (m, 24H,
pentyl), 0.86 ppm (d, J=7.5 Hz, 12H, pentyl); 13C NMR (100 MHz,
CDCl3): d=150.47, 149.71, 149.09, 147.92, 147.72, 147.68, 147.61, 146.06,
140.93, 139.97, 135.36, 131.47, 131.25, 131.00, 128.99, 128.81, 122.59,
122.05, 121.70, 120.93, 119.86, 53.67, 34.19, 34.10, 31.71, 31.78, 30.90,
30.84, 28.86, 23.92, 21.57, 13.28 ppm; MS (MALDI-TOF): m/z calcd for
C170H196N8Zn2: 2477.6 [M]+; found: 2480.4; elemental anal. calcd. (%) for
C170H196N8Zn2: C 82.26, H 7.96, N 4.51; found: C 82.01, H 8.10, N 4.36.
Acknowledgements
We thank Prof. A. Osuka (Kyoto University) for useful discussion. Finan-
cial support by the National Natural Science Foundation of China (Grant
Nos. 21002109, 21073215, 21004072, 21173245, 21172229), the National
Basic Research Program (Grant No. 2010CB934500), and the Chinese
Academy of Sciences is gratefully acknowledged. J.C. thanks the Beijing
Nova Program for financial support.
b,b’-Difluorenone ZnII Porphyrin 6
[1] a) R. W. Wagner, J. S. Lindsey, J. Am. Chem. Soc. 1994, 116, 9759–
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It was prepared by the coupling reaction of 1 with 3,6-dibromofluorenone
(5.0 equiv) according to the general procedure and purified by column
chromatography on silica gel (CH2Cl2/petroleum ether 1:6) and recrystal-
lization from 20% methanol/CH2Cl2 to afford 6 as a red solid in 48%
yield. 1H NMR (400 MHz, CDCl3): d=10.69 (s, 1H, meso), 9.30 (s, 2H,
pyrrole-b), 9.07 (dd, J=10.5, 4.7 Hz, 4H, pyrrole-b), 8.42 (s, 2H, fluore-
none), 8.28 (d, J=7.5 Hz, 2H, fluorenone), 8.18 (d, J=1.6 Hz, 4H, Ar-
H), 8.09 (d, J=1.5 Hz, 2H, Ar-H), 8.03 (d, J=7.6 Hz, 2H, fluorenone),
7.85 (dd, J=10.4, 8.6 Hz, 3H, Ar-H), 7.51–7.41 (m, 6H, fluorenone), 1.58
(s, 36H, tert-butyl), 1.54 ppm (s, 18H, tert-butyl); MS (MALDI-TOF): m/
z calcd for C88H82Br2N4O2Zn: 1453.1 [M]+; found: 1450.4.
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Fluorenone-bridged ZnII Porphyrin Array 7
It was prepared by the coupling reaction of 1 with 6 (1.0 equiv) according
to the general procedure and purified by column chromatography on
silica gel (CH2Cl2/petroleum ether 1:6) and recrystallization from 20%
methanol/CH2Cl2 to afford 7 as a red solid in 22% yield. 1H NMR
(400 MHz, CDCl3): d=9.87 (s, 2H, meso), 8.97 (d, J=8.7 Hz, 12H, pyr-
role-b), 8.20 (s, 4H, fluorenone), 8.12 (s, 2H, Ar-H), 8.05 (s, 4H, Ar-H),
8.01 (s, 4H, Ar-H), 7.97 (d, J=7.6 Hz, 4H, fluorenone), 7.94 (s, 2H, Ar-
H), 7.80 (d, J=7.6 Hz, 4H, fluorenone), 7.76 (s, 2H, Ar-H), 7.74 (d, J=
1.7 Hz, 4H, Ar-H), 1.51–1.40 ppm (m, 108H, tert-butyl); 13C NMR
(100 MHz, CDCl3): d=150.95, 150.58, 148.87, 148.82, 148.75, 148.71,
148.15, 145.25, 144.61, 144.41, 141.75, 141.46, 134.35, 132.68, 132.42,
132.17, 131.97, 129.90, 129.67, 124.54, 123.46, 123.35, 122.57, 121.16, 35.19,
35.10, 31.88, 31.83 ppm; MS (MALDI-TOF): m/z calcd for
C150H152N8O2Zn2: 2226.2 [M]+; found: 2228.1; elemental anal. calcd. (%)
for C150H152N8O2Zn2: C 80.80, H 6.87, N 5.03; found: C 80.24, H 6.98, N
4.88.
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Carbazole-bridged Porphyrin Ring 8
It was prepared by the coupling reaction of 2 with 3,6-dibory-9-ethylcar-
bazole (1.0 equiv) according to the general procedure and purified by
column chromatography on silica gel (CH2Cl2/petroleum ether 1:6) and
recrystallization from 20% methanol/CH2Cl2 to afford 8 as a red solid in
45% yield. 1H NMR (400 MHz, CDCl3): d=10.68 (s, 1H, meso), 9.06 (s,
4H, pyrrole-b), 8.94 (s, 2H, carbazole), 8.90 (s, 2H, pyrrole-b), 8.62 (s,
2H, carbazole), 8.18 (d, J=7.4 Hz, 3H, Ar-H), 8.11 (s, 2H, carbazole),
8.07 (d, J=7.0 Hz, 3H, Ar-H), 8.02 (s, 2H, carbazole), 7.82 (d, J=8.8 Hz,
3H, Ar-H), 7.74 (s, 2H, carbazole), 7.64 (d, J=8.4 Hz, 2H, carbazole),
7.58 (d, J=7.6 Hz, 2H, carbazole), 7.40 (d, J=8.4 Hz, 4H, carbazole),
4.48 (q, J=6.9 Hz, 4H, ethyl), 4.39 (q, J=6.9 Hz, 2H, ethyl), 1.58–
1.48 ppm (m, 63H, tert-butyl and ethyl); 13C NMR (100 MHz, CDCl3):
d=150.67, 150.33, 148.72, 148.60, 148.32, 147.93, 147.64, 142.12, 142.03,
140.32, 139.95, 139.29, 138.16, 135.45, 134.62, 132.44, 132.08, 130.20,
129.78, 129.68, 129.51, 129.46, 126.49, 126.27, 124.83, 124.35, 123.49,
7
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Received: January 10, 2013
Revised: February 4, 2013
Published online: && &&, 0000
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ÝÝ These are not the final page numbers!

FULL PAPER
Do you cross the bridge or do you
fade away: Doubly b-to-b bridged
cyclic ZnII porphyrin arrays with carba-
zole, fluorene, and fluorenone as
bridges were constructed. The incorpo-
ration of bridge units with different
electronic effects results in different
photophysical properties of the cyclic
ZnII porphyrin arrays.
Porphyrinoids
Qingshan Hao, Yi Zeng, Tianjun Yu,
Jinping Chen,* Guoqiang Yang,*
Yi Li*
&&&& — &&&&
Synthesis and Photophysical Proper-
ties of Doubly b-to-b Bridged Cyclic
ZnII Porphyrin Arrays
9
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Chem. Asian J. 2013, 00, 0 – 0
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
These are not the final page numbers! ÞÞ