Design and synthesis of perpendicularly connected metal porphyrin-imide dyads for two-terminal wired single molecular diodes

Article abstract of DOI:10.1002/chem.201402052

Four different porphyrin-imide dyads bearing different central metals (zinc or rhodium) and different substituents on the porphyrin macrocycles (tert-butyl or methoxy) were synthesized for single molecular diode measurements. The molecules were designed to separate the donor component (porphyrin) from the acceptor component (imide) by bonding in a perpendicular arrangement, thus enhancing the rectification properties. UV/Vis absorption spectra and density functional theory calculations showed that the design was successful and that the molecular orbitals of the dyads were the summation of the two components, with minimal interaction between them. The effect of the central metal was found to be significant, with the lowest energy absorption for the zinc dyads being attributed to the mixed state of charge transfer from porphyrin to imide and the Q band, whereas that of the rhodium dyads indicated insignificant charge-transfer character. Molecular diodes: Four types of donor-acceptor molecules based on perpendicularly connected porphyrin and naphthalenediimide having different central metals, zinc(II) and rhodium(III), have been designed and synthesized to create donor-acceptor systems with the desired functionalities for single molecular diodes (see figure). The effects of central metals on molecular orbitals provide strong indications that the Rh porphyrin-imide dyads will show different electronic properties to the Zn molecules.

Full text of DOI:10.1002/chem.201402052

DOI: 10.1002/chem.201402052
Full Paper
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Molecular Devices
Design and Synthesis of Perpendicularly Connected Metal
Porphyrin–Imide Dyads for Two-Terminal Wired Single Molecular
Diodes
Murni Handayani, Syun Gohda, Daisuke Tanaka, and Takuji Ogawa*[a]
Abstract: Four different porphyrin–imide dyads bearing dif-
ferent central metals (zinc or rhodium) and different sub-
stituents on the porphyrin macrocycles (tert-butyl or me-
thoxy) were synthesized for single molecular diode measure-
ments. The molecules were designed to separate the donor
component (porphyrin) from the acceptor component
(imide) by bonding in a perpendicular arrangement, thus en-
hancing the rectification properties. UV/Vis absorption spec-
tra and density functional theory calculations showed that
the design was successful and that the molecular orbitals of
the dyads were the summation of the two components,
with minimal interaction between them. The effect of the
central metal was found to be significant, with the lowest
energy absorption for the zinc dyads being attributed to the
mixed state of charge transfer from porphyrin to imide and
the Q band, whereas that of the rhodium dyads indicated in-
significant charge-transfer character.
ing attributes.[1] Single molecular diodes,[2] one of the funda-
mental devices for molecular electronics, can be achieved by
providing a reliable and symmetric contact between non-sym-
metric donor–acceptor (DA) moieties between two electrodes
in single molecule junctions. The most reliable methods for
Introduction
Molecular electronic devices have been attracting great atten-
tion in the field of nanotechnology owing to their many po-
tential applications, in addition to their fundamentally interest-
Figure 1. Single molecular junctions of the porphyrin–imide dyads for (a) mechanical break junctions and (b) SWNT junctions.
[a] M. Handayani, S. Gohda, Dr. D. Tanaka, Prof. T. Ogawa
measuring single molecular electronic properties are regarded
Department of Chemistry
to be the mechanically controllable break junction technique
(MCBJ)[1a,3] and the scanning tunneling microscope (STM) break
junctions method.[4] In these methods, two anchoring groups
of the molecules are covalently connected to two metal elec-
trodes, forming metal–molecule–metal junctions that enable
evaluation of charge transport through the molecule.[4a] Anoth-
Graduate School of Science
Osaka University, 1-1 Machikaneyama-cho
Toyonaka, Osaka 560-0043 (Japan)
Fax: (+81)668505395
E-mail: ogawa@chem.sci.osaka-u.ac.jp
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201402052.
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Table 1. Molecular orbitals of the porphyrin–imide dyads, as calculated by DFT.[a]
ZTPI (1) ZMPI (2)
RTPI (3)
RMPI (4)
LUMO 3
LUMO 2
LUMO 1
LUMO
HOMO
HOMO 1
HOMO 2
HOMO 3
[a] Calculated with B3LYP/6-311G in the Gaussian 09 program.
er possible approach is to use carbon nanotube (CNT) wiring
to the single molecules,[5] as such structures are unique in
being electrically conductive with a diameter on the molecular
scale. In addition, graphene has been recently developed as
electrodes to build molecular electronic devices by covalently
attaching molecules between one graphene point contact to
another, which forms stable molecular devices in high connec-
tion yields and can tolerate large changes in the environ-
ments.[6]
However, this is a controversial requirement because the s-in-
sulator will raise the tunneling resistance of the molecules, and
p-electronic systems do not allow for efficient electronic sepa-
ration of the donor and acceptor. A perpendicularly connected
DA system has the potential to overcome this problem, with
the steric requirements of the individual donor and acceptor
components preventing them from resonating, and the tunnel-
ing resistance not being raised as there is no insulator part
present. Thus, the molecules are expected to show good recti-
fication performance.
In the original proposal by Aviram and Ratner, a single mo-
lecular diode should have the structure D-s-A, in which s repre-
sents a sigma-bonding insulator.[2b] In some subsequent stud-
ies, D-p-A-type molecules have been employed, in which p de-
notes a p-electronic system.[2a,4a] One essential attribute for
such systems is that the donor and acceptor must be isolated
from each other to realize Aviram and Ratner’s specifications.
Therefore, in the present paper, we have designed and syn-
thesized DA dyads based on porphyrin as the donor and naph-
thalene diimide as the acceptor to create DA molecules with
the desired functionalities for single molecular diodes. We de-
veloped the synthesis of a series of porphyrin–imide dyads
that have hydroxyl groups at both ends for connecting to car-
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boxylic acids at the ends of single-walled CNTs (SWNTs), to the
point contact of graphene[7] and to the metallic electrodes of
mechanical break junctions.[8] The characteristics of the molec-
ular design are 1) perpendicularly connected donor (porphyrin)
and acceptor (imide) parts that have no insulator between
them, and 2) possible variation of the metallic center within
the porphyrin core to enable tuning of the electronic proper-
ties of the molecule.
tion between the two components,[11] while maintaining
a large dipole moment. To show strong rectification behavior,
the donor part should be electronically isolated from the ac-
ceptor part,[12] with a large dipole moment being essential.[13]
The electronic isolation of the porphyrin and the imide compo-
nents can be indicated by carrying out DFT calculations.[14]
Table 1 shows the calculated molecular orbitals for all of the
target molecules, in which it can be seen that the highest oc-
cupied molecular orbital (HOMO) is located on the porphyrin
part, and the lowest unoccupied molecular orbital (LUMO) is
located on the imide part, for all of the synthesized com-
pounds. This indicates that both the HOMO and the LUMO are
highly localized on each component, and confirm strong spa-
tial localization on either the donor or acceptor.
Results and Discussion
We designed four different porphyrin–imide dyads containing
two different central metals, ZnII and RhIII, with different sub-
stituents on the 5 and 15-aryl functional groups of the porphy-
rin (tert-Bu and OMe), as depicted in Figure 1. According to
density functional theory (DFT) calculations, the central metal
greatly affected the electronic properties of the molecules,
which should therefore be observed in the single molecular
current–voltage (I–V) measurements. Two different substituents
were introduced into the structure to assess their effect on the
electronic properties of the single molecules. Hydroxyl groups
at both ends of the molecules are essential for connecting
them covalently to the metal electrodes in electromigrated[9]
or mechanical break junction[1a,4c,10] and STM break junction
methods,[4b,c] as well as to CNT electrodes[1c,5a] for forming
single molecular junctions (Figure 1).
Interestingly, the LUMO 1, HOMO 2, and HOMO 3 of the Rh
porphyrin dyads (3 and 4) are entirely localized on the central
metal, whereas in the Zn porphyrin dyads (1 and 2), no orbitals
are centered at the metal within these energy regions. The
HOMO–LUMO gap energies of the Zn porphyrin dyads (1.43 eV
for 1 and 1.41 eV for 2) are significantly smaller than those of
the Rh porphyrin dyads (1.69 eV for both 3 and 4). This pro-
vides a strong indication that the Rh porphyrin dyads will
show different I–V characteristics to the Zn molecule. The ef-
fects of substituents on the porphyrin of the dyads (tBu and
OMe) on the molecular orbitals were observed in HOMO 2 and
HOMO 3 of the Zn porphyrin dyads.
Design and DFT calculations of the target molecules
Synthesis of the molecules
One important feature of the porphyrin–imide dyads is that
the donor porphyrin is directly linked to the acceptor imide
with perpendicular arrangement (Figure 1). This is necessary to
achieve the steric hindrance required for minimizing conjuga-
The porphyrin–imide core was prepared as shown in
Scheme 1. One of the most important stages in the synthesis
of non-symmetric molecules is the introduction of a non-sym-
metric structure into a symmetric starting material. In the pres-
Scheme 1. Preparation for porphyrin–imide complex from the free-based porphyrin.
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ent synthesis, this step involved the incorporation of a nitro
group into 5,15-diarylporphyrin. Electrophilic nitration of the
free base porphyrins (6a and 6b) with the mild nitrating re-
agent, NaNO2 with trifluoroacetic acid (TFA), for 1 h, afforded
the mono-nitrated products (7a and 7b) in good yields (79
and 88%, respectively). The nitro porphyrins were subsequent-
ly reduced to the corresponding amino porphyrins by SnCl2,[15]
resulting in the formation of 8a and 8b in 76 and 80% yield,
respectively. These were then condensed with monoimide 10
to give porphyrin–imides 11 a and 11 b in 46 and 49% yield,
respectively. The non-symmetric naphthalene-monoimide 10
was prepared in 37% yield by condensation of naphthalene-
tetracarboxylic dianhydride with O-protected aminophenol 9
in the presence of 1-ethyl-3-(3-dimethylaminopropyl)carbodi-
imide (EDC). Bromination at the meso position of porphyrin–
imides 11 a and 11 b was performed using N-bromosuccini-
mide (NBS) to give 12a and 12b in 98% yield for both com-
pounds, respectively. Another anchoring hydroxyl group was
introduced using Sonogashira coupling of bromides 12 with
alkyne derivative 15, providing 16a and 16b in 57 and 75%
yield, respectively.
Target ZnII porphyrin–imides 1 and 2 were obtained by
cleaving the tert-butyldiphenylsilyl (TBDPS) protecting group
using tetrabutylammonium fluoride solution (TBAF), giving
yields of 95 and 94%, respectively (Scheme 2). The structures
were verified using 1H/13C NMR spectroscopy, UV/Vis, MALDI-
TOF mass spectroscopy, and high resolution mass spectrosco-
py (HRMS-ESI) that were strongly characteristic of the target
molecules (see the Supporting Information).
RhIII iodide porphyrin–imides 18 were prepared through de-
metalation of ZnII porphyrin–imides 16a and 16b using tri-
fluoroacetic acid, yielding free base porphyrin–imides 17a and
17b in 87% yield for both compounds. Demetalation was
Scheme 2. Formation for target compounds of zinc(II) and rhodium(III) por-
phyrin–imide dyads.
1
marked with inner NH protons emerging in the H NMR spec-
tra of 17a or 17b at about d=À2.21 ppm (2H). Rh metalation
was achieved by using [Rh2(CO)4Cl2] and iodine, giving 18a
and 18b in yields of 74 and 97%, respectively.
The Soret band for 1 (442 nm, e=342000) was found to be
almost the same as that of the porphyrin component alone
(448 nm, e=95500 for ZnII (5-(2-(4’-dimethylaminophenyl)-
ethynyl)-10, 20-diphenylporphyrinate).[16] The absorption by
the imide moiety was almost the same for 1 (359 and 376 nm),
3 (359 and 379 nm), and 10 (353 and 372 nm). These results
show that the electronic systems of the porphyrin and imide
components within the dyads were well isolated as planned.
The DFT calculations also support this conclusion. The fron-
tier orbital correlation diagram for 1–4, and the porphyrin and
imide components alone is shown in Figure 3. Within the fron-
tier orbitals, no hybrid orbitals appeared to be generated in
the porphyrin–imide dyads, with those that were present
being due to a simple summation of the porphyrin and imide
components. The energies of the orbitals of the imide compo-
nent increased in the dyads, and those from the porphyrin
component decreased, which can be rationalized by the induc-
tive effects of each component; that is, the electron-rich por-
phyrin component raises the orbital energies of the electron-
poor imide component, and the latter reduces the former by
electrostatic interactions.
Target molecules 3 and 4 bearing rhodium(III) as the central
metal in the porphyrin ring, and hydroxyl groups at both ends,
were accomplished by detaching the TBDPS protecting
groups, giving yields of 96 and 90%, respectively (Scheme 2).
1
The structures of 3 and 4 were verified by using H/13C NMR
spectroscopy, MALDI-TOF MS, HRMS, and elemental analysis,
which clearly indicated the features of target compounds 3
and 4.
Electronic structure evaluation of the porphyrin–imide
dyads by using spectroscopy and DFT calculations
The absorption spectra of dyads 1 and 3 in a number of differ-
ent solvents are shown in Figure 2. The absorption spectra of
1, 3, 6a, and 10 in CH2Cl2, along with their molar absorption
coefficients, are given in the Supporting Information (Fig-
ure S47).
These molecules were designed to achieve electrical isola-
tion of the porphyrin and imide moieties by bonding them in
a perpendicular manner so as to prevent strong conjugation.
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Figure 3. Frontier orbital correlation diagram for compounds 1–4 and relat-
ed molecules. The blue lines are occupied molecular orbitals and the red
lines are unoccupied molecular orbitals. The broken lines indicate the corre-
lation of the dyads with the porphyrin and imide components. The arrows
indicate transitions between the orbitals calculated using TD-DFT.
the Zn porphyrin were higher than those of the Rh porphyrin,
as shown in Figure 3. Thus, the more electron-donating Zn
porphyrin component would produce a stronger CT character
when connected with the imide component, whereas the less
electron-donating Rh porphyrin component would only afford
weak or no CT character in the dyads. Such a precise difference
could not be reproduced by the TD-DFT calculations, as has
been reported previously.[17]
Figure 2. UV/Vis absorption spectra of porphyrin–imide dyads 1 and 3 in
CH2Cl2, DMF, and CH3CN.
Conclusion
According to the time-dependent (TD)-DFT calculations,
HOMO to LUMO (porphyrin to imide) transitions in dyads
1 and 3 are forbidden, and the oscillator strengths (f) for the
corresponding transitions are zero, which is because of the
perpendicular alignment of the porphyrin and imide compo-
nents. For both dyads, the lowest transition is predicted to be
from HOMO 1 (porphyrin p-system) to LUMO (imide), which is
a charge-transfer (CT) state. A summary of the TD-DFT calcula-
tions is shown in the Supporting Information.
We successfully synthesized four different porphyrin–imide
dyads with anchoring hydroxyl functional groups at both ends
for single molecular diode measurements. From the optical ab-
sorption spectra and DFT calculations, the porphyrin and imide
components appeared to be electronically separated, as de-
signed. The effect of the central metal within the porphyrin
component on the electronic properties of the dyad was
found to be considerable. The Zn dyad showed a high level of
CT character, whereas the Rh dyad showed none, which would
be expected to affect the single molecular electronic proper-
ties of these dyads. Measurements of the single molecular I–V
curves are in progress and will be reported in due course.
However, these calculations are not consistent with the ob-
served solvent effect that occurred for Rh dyad 3. As shown in
Figure 2, the low-energy absorption bands of the Zn dyad
1 shifted to longer wavelengths in more polar solvents, being
observed at 563 and 614 nm in CH2Cl2, 575 and 631 nm in
DMF, and 581 and 650 nm in CH3CN, which is consistent with
CT character. In contrast, the Rh dyad 3 showed little solvent
effect, with bands at 548 and 601 nm in CH2Cl2, 548 and
597 nm in DMF, and 552 and 602 nm in CH3CN. This is likely
because of the difference in the electron-donating ability of
the two porphyrin components; the HOMO–LUMO levels of
Experimental Section
General methods
All reagents and solvents were of analytical grade and were used
without further purification. All reactions were performed under
dry N2. The reported melting points are uncorrected. All glassware
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1
was dried in an oven at 908C prior to use. H NMR spectra were re-
5,15-Bis(4-tert-butylphenyl)-10-nitroporphyrin
(7a):[20]
TFA
corded using 400 and 500 MHz NMR spectrometers using tetrame-
thylsilane (TMS) as an internal standard. UV/Vis absorption spectra
were recorded on a Shimadzu UV-3100 double-beam spectropho-
tometer.
(42 mL) was added to a solution of porphyrin 6a (779 mg,
1.36 mmol) in CH2Cl2 (48 mL). After stirring for a few min, NaNO2
(94 mg, 1.36 mmol) was added and the solution was stirred for
a further hour. After complete consumption of 6a, the reaction
mixture was neutralized with aq. NaHCO3. The organic layer was
separated, washed twice with H2O, and evaporated to give 7a.
This was then purified by silica gel column chromatography using
CH2Cl2 as the eluent, to give a dark-purple solid (662 mg, 79%).
DFT calculations
The Gaussion 09 package was used for all of the calculations.[14]
The calculations of molecular orbitals of the four target com-
pounds were carried out using DFT at the b3Lyp/6–311G (2d, p)
level for C, H, O, N, and Zn atoms, and the b3Lyp/3–21*G level for
Rh and I atoms, with full structure optimizations. For TD-DFT calcu-
lations, structures were optimized using the above basis sets, and
single-point calculations were performed using 6–311+ +G for C,
H, O, N, and Zn atoms, and 3–21*G for Rh and I atoms.
1
M.p.>3008C; H NMR (400 MHz, CDCl3, 258C, TMS): d=10.29 (1H,
s, meso-H), 9.33–9.31 (4H, m, b-pyrrole-H), 9.09 (2H, d, J=5.2 Hz, b-
pyrrole-H), 9.03 (2H, d, J=4.8 Hz, b- pyrrole-H), 8.14 (4H, d, J=
7.6 Hz, aryl-H), 7.82 (4H, d, J=7.6 Hz, aryl-H), 1.63 (18H, s, tert-
butyl-H), À2.92 ppm (2H, s, NH); 13C NMR (125 MHz, CDCl3, 258C,
TMS): d=31.67, 34.96, 108.66, 122.28, 124.09, 124.24, 124.74,
127.97, 129.13, 130.29, 131.80, 132.24, 133.24, 134.54, 137.66,
151.11 ppm; UV/Vis (CH2Cl2): lmax =415, 513, 551, 585, 641 nm; MS
(MALDI-TOF): m/z calcd for C40H37N5O2: 619.29; found: 618.6 [M+];
HRMS (ESI-TOF) m/z: calcd for C40H38N5O2: 620.3020 [M+H+];
found: 620.3026.
Syntheses of the compounds
Dipyrromethane (5): We synthesized 5 using a previously reported
method with slight modifications.[18] Paraformaldehyde (3.46 g,
0.11 mol) and pyrrole (200 mL, 2.88 mol) were placed into a three-
necked round bottomed-flask. The mixture was then heated at
908C until the paraformaldehyde was completely dissolved, and
then trifluoroacetic acid (TFA; 0.89 mL) was added. The reaction
was allowed to proceed for 15 min, then the solution was treated
with aq. NaOH solution, followed by extraction with AcOEt using
a separator funnel. The organic layer was washed twice with aq.
NaCl and then dried over Na2SO4. The solution was filtered and
then extracted with hot hexane. The product was purified by re-
crystallization from EtOH/H2O (1:1), yielding colorless crystals (6.9 g,
41%): 1H NMR (400 MHz, CDCl3, 258C, TMS): d=7.77 (2H, brs),
6.63–6.62 (2H, m), 6.15–6.13 (2H, q, J=2.8 Hz), 6.03–6.02 (2H, m),
3.95 ppm (2H, s).
5,15-Bis(4-methoxylphenyl)-10-nitroporphyrin (7b): Nitropor-
phyrin 7b was prepared using the same method as was employed
for the synthesis of 7a, but with 6b (116 mg, 0.9 mmol) as the
starting material, giving a dark-purple solid (114 mg, 88%). M.p.
3308C; 1H NMR (400 MHz, [D7]DMF, 258C, TMS): d=10.80 (1H, s,
meso-H), 9.71 (2H, d, J=4.4 Hz, b-pyrrole-H), 9.45 (2H, d, J=5.2 Hz,
b-pyrrole-H), 9.17 (2H, d, J=4.8 Hz, b-pyrrole-H), 9.10 (2H, d, J=
4.8 Hz, b-pyrrole-H), 8.27 (4H, d, J=8.4 Hz, aryl-H), 7.51 (4H, d, J=
8.4 Hz, aryl-H), 4.16 (6H, s, methoxy-H), À2.91 ppm (2H, s, NH);
13C NMR (100 MHz, [D7]DMF, 258C, TMS): d=55.79, 109.86, 113.33,
122.50, 128.02, 128.09, 129.29, 130.53, 132.00, 132.88, 133.63,
133.76, 136.31, 160.42, 162.76, 162.92 ppm; UV/Vis (CH2Cl2): lmax
=
415, 513, 550, 585, 642 nm; MS (MALDI-TOF): m/z calcd for
C34H25N5O4: 567.19 [M+]; found: 568.5 [M+H+]; elemental analysis
calcd (%) for C34H25N5O4: C 71.95; H 4.44; N 12.34; found: C 71.89;
H 4.55; N 11.94.
5,15-Bis(4-tert-butylphenyl)porphyrin (6a): 4-tert-Butylbenzalde-
hyde (1.38 mL, 8.25 mmol) was added to a solution of 5 (1.20 g,
8.22 mmol) in degassed CH2Cl2 (2 L), and the flask was shielded
from ambient light. TFA (140 mL, 1.8 mmol) was added to the solu-
tion and it was stirred for 20 h, followed by addition of p-chloranil
(3 g, 12.2 mmol) and further stirring for 2 h. Et3N (6 mL) was then
added, followed by silica gel, and the mixture was evaporated to
give a powder containing the product, which was applied to flash
column chromatography. The eluent was evaporated, and the
product was recrystallized from a small amount of CH2Cl2 and
excess MeOH to give crystals, which were separated by filtration.
The crystals were washed with acetone and CH2Cl2 and then dried
in vacuo to obtain a purple amorphous solid (1.37 g, 58%). M.p.>
3008C; 1H NMR (400 MHz, CDCl3, 258C, TMS): d=10.31 (2H, s,
meso-H), 9.40 (4H,d, J=4.8 Hz, b-pyrrole-H), 9.14 (4H, d, J=4.4 Hz,
b-pyrrole-H), 8.21 (4H, d, J=8.0 Hz, aryl-H), 7.83 (4H, d, J=8.4 Hz,
aryl-H), 1.64 (18H, s, tert-butyl-H), À3.08 ppm (2H, s). This com-
pound was not soluble enough to be analyzed by 13C NMR spec-
troscopy. UV/Vis (CH2Cl2): lmax =408, 504, 539, 577, 631 nm; MS
(MALDI-TOF) m/z: calcd for C40H38N4 [M+]: 574.31; found 573.0
[MÀH+]; HRMS (ESI-TOF): m/z calcd for C40H39N4: 575.3169
[M+H+]; found: 575.3173.
5,15-Bis(4-tert-butylphenyl)-10-aminoporphyrin (8a):[20] Conc. HCl
(12m, 30 mL) was added slowly to a solution of 7a (278 mg,
0.49 mmol) and SnCl2 (1.05 g, 5.5 mmol) in dry Et2O (150 mL), fol-
lowed by heating the solution at reflux for about 10 h. The mixture
was then carefully neutralized with aq. NaOH (5%) and the precipi-
tated product was filtered to give a green solid (202 mg, 76%).
1
M.p.>3508C; H NMR (400 MHz, CDCl3, 258C, TMS): d=9.35 (1H,
s, meso-H), 9.05 (2H, d, J=4.4 Hz, b-pyrrole-H), 8.86 (2H, d, J=
4.8 Hz,b-pyrrole-H),8.70 (2H, d, J=4.4 Hz, b-pyrrole-H), 8.60 (2H, d,
J=4.8 Hz, b-pyrrole-H), 8.06 (4H, d, J=8.0 Hz, aryl-H), 7.74 (4H, d,
J=8.0 Hz, aryl-H), 6.44 (2H,s, NH), 1.60 (18H, s, tert-butyl-H),
À0.88 ppm (2H, s, NH). This compound was not stable enough to
analyze by using 13C NMR spectroscopy. UV/Vis (CH2Cl2): lmax =421,
502, 533, 573, 675 nm; MS (MALDI-TOF): m/z calcd for C40H39N5
589.32 [M+]; found: 589.7; HRMS (ESI-TOF): m/z calcd for C40H40N5:
590.3278 [M+H+]; found: 590.3281.
5,15-Bis(4-methoxyphenyl)-10-aminoporphyrin (8b): Concentrat-
ed HCl (12m, 30 mL) was added slowly to a solution of 7b
(510 mg, 0.9 mmol) and SnCl2 (2.0 g, 10.5 mmol) in dry Et2O
(300 mL). After heating at reflux for about 10 h, the mixture was
carefully neutralized with aq. NaOH (5%), and the precipitated
product was filtered to give a green solid (387 mg, 80%): M.p.>
4008C; 1H NMR (400 MHz, [D7]DMF, 258C, TMS): d=9.52 (2H, d,
J=4.4 Hz), 9.15 (1H, s, meso-H), 8.83 (2H, d, J=4.4 Hz, b-pyrrole-H),
8.82 (2H, s, b-pyrrole-H), 8.46 (2H, d, J=4.8 Hz, b-pyrrole-H), 8.28
(2H, d, J=4.8 Hz, b-pyrrole-H), 8.03 (4H, d, J=2.0 Hz, aryl-H), 7.37
(4H, d, J=8.8 Hz, aryl-H), 4.09 (6H, s, methoxy-H), 0.39 ppm (2H, s,
5,15-Bis(4-methoxylphenyl)porphyrin (6b):[19] Compound 6b was
synthesized by using a similar method to that employed for 6a,
giving purple amorphous crystals (2.1 g, 39%). M.p.>3308C;
1H NMR (400 MHz, CDCl3, 258C, TMS): d=10.29 (2H, s, meso-H),
9.38 (4H, d, J=5 Hz, b-pyrrole-H), 9.10 (4H, d, J=5 Hz, b-pyrrole-
H), 8.03–8.16 (4H, m, aryl-H),7.26–7.34 (4H, m, aryl-H), 4.13 (6H, s,
methoxy-H), À3.06 (2H, brs, NH); UV/Vis (CH2Cl2): lmax =410, 504,
540, 578, 634 nm.
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NH); 13C NMR (100 MHz, [D7]DMF, 258C, TMS): d=55.64, 110.31,
112.95, 116.70, 119.60, 129.47, 133.62, 134.25, 134.84, 135.32,
156.08, 163.15, 165.95 ppm; UV/Vis (CH2Cl2): lmax =361, 377, 443,
566, 616 nm; MS (MALDI-TOF) m/z: calcd for C76H62N6O5SiZn:
1230.4 [M+]; found: 1230.3; HRMS (ESI-TOF): m/z calcd for
C76H62N6O5SiZn: 1230.3842 [M+]; found: 1230.3839.
135.36, 136.28, 138.81, 139.20, 159.80 ppm; UV/Vis (CH2Cl2): lmax
=
420, 502, 533, 573, 620, 675 nm; MS (MALDI-TOF): m/z calcd for
C34H27N5O2: 537.22 [M+]; found: 538.3 [M+H+]; elemental analysis
calcd (%) for C34H27N5O2 +0.7H2O (hygroscopic): C 74.22; H 5.20; N
12.73; found: C 74.15; H 4.97; N 12.51.
ZnII-5,15-bis(4-methoxyphenyl)-10-(N-(4-tert-butyldiphenylsil-
yloxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicarboxy-
imide)porphyrin (11b): A solution of 8b (600 mg, 1.12 mmol) and
10 (680 mg, 1.18 mmol) in dry DMF (80 mL) was heated at around
1008C for about 48 h. The solvent was then removed by rotary
evaporation, the residue was dissolved in CH2Cl2 (200 mL), and
[Zn(OAc)2]·2H2O (1.5 g) was added. After stirring for about 10 h,
the solvent was removed and the residue purified by silica gel
column chromatography (CH2Cl2) to give a dark-purple solid
4-tert-Butyldiphenylsilyloxyaniline (9): A solution of 4-aminophe-
nol (4 g, 36 mmol), imidazole (5 g, 73 mmol) and tert-butyldiphe-
nylchlorosilane (9.6 mL, 36.4 mmol) in dry CH2Cl2 (400 mL) was
stirred for about 48 h. The solvent was removed and the residue
was purified by silica gel column chromatography (CH2Cl2) to give
1
a light-orange liquid (12.4 g, 97%). H NMR (400 MHz, CDCl3, 258C,
1
TMS): d=7.72–7.70 (4H, m, ortho-H of phenylsilyl), 7.42–7.32 (6H,
m, meta-H and para-H of phenylsilyl), 6.57 (2H, d, J=16.0 Hz, aryl-
H), 6.47 (2H, d, J=16.0 Hz, aryl-H), 3.31 (2H, br, NH), 1.08 ppm (9H,
s, tert-butyl-H); 13C NMR (100 MHz, CDCl3, 258C, TMS): d=19.49,
26.64, 116.93, 120.14, 127.59, 129.67, 133.1, 134.71, 135.46,
149.06 ppm; UV/Vis (CH2Cl2): lmax =229, 305 nm; MS (MALDI-TOF):
m/z calcd for C22H25NOSi: 347.2; found: 347.7 [M+]; elemental anal-
ysis calcd (%) for C22H25NOSi: C 76.03; H 7.25; N 4.03; found: C
76.01; H 7.23; N 3.92.
(64.5 mg, 49%): M.p. 2208C; H NMR (400 MHz, CDCl3, 258C, TMS):
d=9.98 (1H, s, meso-H), 9.17 (2H,d, J=4.4 Hz, b-pyrrole-H), 9.01–
8.98 (6H, m, b-pyrrole-H), 8.91 (4H, s, imide-H), 8.05 (4H,d, J=
8.4 Hz, aryl-H), 7.80–7.78 (4H, m, ortho-H of phenylsilyl), 7.49–7.40
(6H, m, meta-H and para-H of phenylsilyl), 7.23 (4H, m, aryl-H),
7.11–7.09 (2H, m, aryl-H), 7.00–6.97 (2H, m, aryl-H), 4.02 (6H, s, me-
thoxy-H), 1.17 ppm (9H, s, tert-butyl); 13C NMR (100 MHz, CDCl3,
258C, TMS): d=19.62, 26.61, 55.58, 109.72, 112.11, 120.40, 120.53,
120.89, 127.08, 127.24, 127.45, 127.45, 127.86, 128.01, 129.12,
129.19, 129.99, 130.03, 130.93, 131.59, 131. 89, 131.99, 132.54,
133.93, 134.65, 135.51, 147.90, 149.41, 150.51, 150.97, 159.17,
162.14, 163.02, 165.76 ppm; UV/Vis (CH2Cl2): lmax =308, 361, 367,
416, 542, 616 nm; MS (MALDI-TOF) m/z calcd for C70H50N6O7SiZn:
1178.3 [M+]; found: 1180.4 [M+2H+]; elemental analysis calcd (%)
for C70H50N6O7SiZn: C 71.21; H 4.27; N 7.12; found: C 70.90; H 4.51;
N 7.06.
ZnII-1-bromo-5,15-bis(4-tert-butylphenyl)-10-(N-(4-tert-butyldi-
phenylsilyloxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicar-
boxyimide)porphyrin (12a):[21] NBS (12.7 mg, 0.07 mmol) was
added to a solution of 11 a (90 mg, 0.07 mmol) in dry CH2Cl2
(800 mL) at 08C, and stirred for about 10 h at the same tempera-
ture. The solvent was removed and the residue was purified by
silica gel column chromatography (CH2Cl2/AcOEt) to afford a dark-
purple solid (96 mg, 98%): M.p.>3508C (decomposed); 1H NMR
(400 MHz, CDCl3, 258C, TMS): d=9.77 (2H,d, J=4.8 Hz, b-pyrrole-
H), 9.03–8.96 (6H, m, b-pyrrole-H), 8.99 (4H,s, imide-H), 8.08
(4H,d,J=8.0 Hz, aryl-H), 7.81–7.79 (4H, m, aryl-H),7.76–7.74 (4H, d,
J=8.4 Hz, ortho-H of phenylsilyl), 7.45–7.43 (6H,m, meta-H and
para-H of phenylsilyl), 7.12 (2H, d, J=8.4 Hz, aryl-H), 7.00 (2H, d,
J=8.0 Hz, aryl-H), 1.61 (18H, s, tert-butyl-H), 1.16 ppm (9H, s, tert-
butyl-H); 13C NMR (125 MHz, CDCl3, 258C, TMS): d=19.54, 26.52,
31.69, 34.90, 120.59, 122.55, 123.55, 127.00, 127.19, 127.53, 127.93,
128.04, 129.20, 130.11, 131.68, 132.11, 132.51, 133.09, 133.47,
134.32, 134.62, 135.57, 139.02, 148.85, 149.54, 150.56, 150.80,
151.47, 156.09, 163.11, 165.73 ppm; UV/Vis (CH2Cl2): lmax =361, 371,
N-(4-tert-Butyldiphenylsilyloxyphenyl)naphthalene-1,8-dicarbox-
yanhydride-4,5-dicarboxyimide (10): A cold solution of com-
pound 9 (2.32 g, 6.67 mmol) in dry DMF (15 mL) was added to a so-
lution of 1,4,5,8-naphthalenetetracarboxylic dianhydride (2.82 g,
10.5 mmol) and EDC (800 mg, 4.2 mmol) in dry DMF (25 mL) at
1208C. The mixture was stirred at 1208C for about 24 h. The sol-
vent was removed in vacuo and the residue was purified by silica
gel column chromatography (CH2Cl2/hexane) to give a light-yellow
solid (2.9 g, 37%): M.p. 2508C; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d=8.83 (4H, s, imide-H), 7.77–7.75 (4H, m, ortho-H of phe-
nylsilyl), 7.45–7.40 (6H, m, meta-H and para-H of phenylsilyl), 7.03
(2H, d, J=8.8 Hz, aryl-H), 6.93 (2H, d, J=12.0 Hz, aryl-H), 1.14 ppm
(9H, s, tert-butyl); 13C NMR(100 MHz, CDCl3, 258C, TMS): d=19.56,
26.55, 120.51, 122.93, 126.87, 127.79, 127.82, 128.01, 128.86,
129.02, 130.00, 131.41, 132.40, 133.09, 135.44, 156.05, 158.64,
162.33 ppm; UV/Vis (CH2Cl2): lmax =223, 270, 352, 371 nm; MS
(MALDI-TOF): m/z calcd for C36H27NO6Si: 597.2 [M+]; found: 598.1
[M+H+]; elemental analysis calcd (%) for C36H27NO6Si: C 72.34; H
4.55; N 2.34; found: C, 72.09; H 4.58; N 2.49.
ZnII-5,15-bis(4-tert-butylphenyl)-10-(N-(4-tert-butyldiphenylsil-
yloxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicarboxy-
imide)porphyrin (11a): A solution of aminoporphyrin 8a (243 mg,
0.41 mmol) and 10 (257 mg, 0.43 mmol) in dry DMF (30 mL) was
heated at around 1008C for about 10 h. The solvent was then re-
moved by rotary evaporation, the residue was dissolved in CH2Cl2
(50 mL), and [Zn(OAc)2]·2H2O (2 g) was added. After stirring for
about 24 h, the solvent was allowed to evaporate at room temper-
ature, and the residue was purified by using silica gel column chro-
matography (CH2Cl2) to give a dark-purple solid (231 mg, 46%).
422,
456,
552,
591 nm;
MS
(MALDI-TOF):
m/z calcd for C76H61BrN6O5SiZn: 1308.3 [M+]; found: 1308.8; HRMS
(ESI-TOF): m/z: calcd for C76H61BrN6O5SiZn: 1308.2948 [MÀH+];
found: 1308.2922.
1
M.p.>3008C; H NMR (400 MHz, CDCl3, 258C, TMS): d=10.29 (1H,
s, meso-H), 9.39 (2H, d, J=4.4 Hz, b-pyrrole-H), 9.12 (2H, d, J=
4.8 Hz, b-pyrrole-H), 9.08 (4H, s, imide-H), 9.02 (2H, d, J=7.6 Hz, b-
pyrrole-H), 8.98 (2H, d, J=7.2 Hz, b-pyrrole-H), 8.13 (4H, d, J=
8.0 Hz, aryl-H), 7.81–7.75 (8H, m, aryl-H and ortho-H of phenylsilyl),
7.48–7.42 (6H, m, meta-H and para-H of phenylsilyl), 7.13 (2H, d,
J=8.4 Hz, aryl-H), 6.99 (2H, d, J=8.8 Hz, aryl-H), 1.62 (18H, s, tert-
butyl), 1.16 ppm (9H, s, tert-butyl); 13C NMR (125 MHz, CDCl3,
258C, TMS): d=19.53, 26.52, 31.72, 34.88, 120.58, 121.29, 123.52,
126.75, 127.15, 127.23, 127.46, 127.58,127.89,127.94, 128.07, 129.22,
130.11, 131.69, 131.80, 132.09, 132.51, 132.67, 134.12, 134.45,
135.53, 135.57, 139.29, 147.87, 149.31, 150.29, 150.33, 150.81,
ZnII-1-bromo-5,15-bis(4-methoxyphenyl)-10-(N-(4-tert-butyldi-
phenylsilyloxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicar-
boxyimide)porphyrin (12b): Bromide 12b was obtained in a simi-
lar manner to 12a, but with 11 b (83 mg, 0.13 mmol) as the start-
ing material, giving a dark-purple solid (88 mg, 98%): M.p. 2408C;
1H NMR (400 MHz, CDCl3, 258C, TMS): d=9.67 (2H,d, J=4.4 Hz, b-
pyrrole-H), 8.97–8.89 (6H,m, b-pyrrole-H), 8.91 (4H, s, imide-H), 8.02
(4H, d, J=8.4 Hz, aryl-H), 7.80–7.78 (4H, m, ortho-H of phenylsilyl),
7.49–7.40 (6H, d, meta-H and para-H of phenylsilyl), 7.22 (4H, d,
J=8.4 Hz, aryl-H), 7.11–7.09 (2H, m, aryl-H), 6.99–6.96 (2H, m, aryl-
H), 4.07 (6H, s, methoxy-H), 1.17 ppm (9H, s, tert-butyl-H); 13C NMR
Chem. Eur. J. 2014, 20, 1 – 11
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(100 MHz, CDCl3, 258C, TMS): d=19.61, 26.61, 55.54, 106.21,
112.09, 120.52, 121.89, 126.85, 127.08, 127.13, 127.41, 127.59,
127.88, 129.15, 129.51, 130.04, 131.55, 131.98, 132.52, 132.87,
133.12, 134.28, 134.46, 134.67, 135.37, 135.49, 135.51, 148.67,
149.30, 150.79, 151.41, 155.96, 159.12, 162.92, 165.58 ppm; UV/Vis
(CH2Cl2): lmax =313, 361, 371, 423, 552, 592 nm; MS (MALDI-TOF):
m/z calcd for C70H49BrN6O7SiZn: 1256.2 [M+]; found: 1257.0 [M+
H+]; elemental analysis calcd (%) for C70H49BrN6O7SiZn: C 66.75; H
3.92; Br 6.34; N 6.67; found: C 66.58; H 4.03; N 6.43.
Ethynylporphyrin 16b was prepared in a similar manner to 16a,
but with 12b (200 mg, 0.16 mmol) as the starting material, giving
a dark-purple solid(183 mg, 75%). M.p. 3388C; H NMR (400 MHz,
1
CDCl3, 258C, TMS): d=9.74 (2H, d, J=4.4 Hz, b-pyrrole-H), 8.97–
8.88 (6H, m, b-pyrrole-H), 8.94 (4H, s, imide-H), 8.05 (4H, d, J=
8.4 Hz, aryl-H), 7.81–7.76 (10H, m, aryl-H and ortho-H of phenylsilyl-
H), 7.47–7.42 (14H, m, aryl-H and meta-H and para-H of phenylsil-
yl), 7.11 (2H, d, J=4.4 Hz, aryl-H), 6.99–6.98 (4H, m, aryl-H), 4.06
(6H, s, methoxy-H), 1.18 (9H, s, tert-butyl-H), 1.17 ppm (9H, s, tert-
butyl-H); 13C NMR (100 MHz, CDCl3, 258C, TMS): d=19.53, 26.53,
55.41, 91.10, 97.01, 102.43, 110.43, 112.00, 116.37, 120.11, 120.41,
122.03, 126.77, 126.85, 127.10, 127.28, 127.35, 127.78, 127.81,
129.07, 129.93, 129.95, 130.84, 130.85, 131.43, 131.84, 132.41,
132.44, 132.60, 132.78, 133.79, 134.39, 135.23, 135.38, 135.41,
148.05, 150.51, 150.70, 151.65, 155.88, 156.05, 159.02, 162.85,
165.46 ppm; UV/Vis (CH2Cl2): lmax =360, 375, 441, 565, 617 nm; MS
(MALDI-TOF): m/z calcd for C94H72N6O8Si2Zn: 1532.4 [M+]; found:
1533.4 [M+H+]; elemental analysis calcd (%) for C94H72N6O8Si2Zn:
C 73.54; H 4.73; N 5.47; found: C 73.25; H 4.83; N 5.34.
4-tert-Butyldiphenylsilyloxyphenylacetylene (15): Dry THF
(75 mL) and Et3N (5 mL) were added to 4-iodophenol (30 mmol),
CuI (1.2 mmol), and [Pd(PPh3)4] (0.60 mmol), followed by stirring for
20 min. Trimethylsilylacetylene (31.5 mmol) was then added drop-
wise and the reaction mixture was stirred for 20 h in the dark. The
solution was then filtered using Celite, and the filtrate was purified
using silica gel column chromatography with CH2Cl2/AcOEt (2:1) as
eluent, giving compound 13 (5.64 g, 99%). The trimethylsilyl group
of 13 was then cleaved by adding TBAF (80 mL) and CHCl3 (1.5 L)
and stirring for 1 h, giving 14 (3.45 g, 97%). A solution of 4-ethy-
nylphenol 14 (3.4 g, 29.2 mmol), imidazole (4.0 g, 58.4 mmol), and
tert-butyldiphenylchlorosilane (9.0 mL, 33.9 mmol) in dry DMF
(200 mL) was stirred for about 24 h. The mixture was then poured
into H2O and extracted with Et2O. The organic layer was washed
with twice with H2O, dried, and evaporated. The product was puri-
fied by silica gel column chromatography (CH2Cl2) to give a yellow
solid (9.1 g, 88%). M.p. 798C; 1H NMR (400 MHz, CDCl3, 258C,
TMS): d=7.70–7.68 (4H, m, ortho-H of phenylsilyl), 7.43–7.35 (6H,
d, meta-H and para-H of phenylsilyl), 7.22 (2H, d, J=8.4 Hz, aryl-H),
6.68 (2H, d, J=8.4 Hz, aryl-H), 2.94 (1H, s, ethynyl-H), 1.09 ppm
(9H, s, tert-butyl); 13C NMR (100 MHz, CDCl3, 258C, TMS): d=19.49,
26.52, 75.86, 83.66, 114.58, 119.75, 127.79, 129.95, 132.39, 133.34,
135.37, 156.05 ppm; UV/Vis (CH2Cl2): lmax =226, 252, 31, 8,
340 ppm; MS (MALDI-TOF): m/z: calcd for C24H24OSi: 356.2 [M+];
found: 357.4 [M+H+]; elemental analysis calcd (%) for C24H24OSi: C
80.85; H 6.78; found: C 80.46; H 6.71.
ZnII-1-(4-hydroxyphenylethynyl)-5,15-bis(4-tert-butylphenyl)-10-
(N-(4-tert-butyldiphenylsilyloxyphenyl)naphthalene-1)-10-(N-(4-
hydroxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicarboxy-
imide)porphyrin (1): 1m TBAF in THF (0.1 mL) was added to a solu-
tion of 16a (101 mg, 0.06 mmol) in dry CH2Cl2 (20 mL) at 08C, and
the mixture was stirred for 1 h. The solvent was removed and the
residue was purified by silica gel column chromatography (CH2Cl2/
MeOH), to give a dark-green solid (67 mg, 95%). M.p.>3508C;
1H NMR (400 MHz, (CD3)2CO, 258C): d=9.85 (2H, d, J=4.4 Hz, b-
pyrrole-H), 9.32 (2H, d, J=4.8 Hz, b-pyrrole-H), 9.01–8.92 (6H, m, b-
pyrrole-H and imide-H), 8.81 (2H, J=4.4 Hz, b-pyrrole-H), 8.69 (1H,
s, OH), 8.16 (4H, d, J=8.4 Hz, aryl-H),7.99 (2H, d, J=9.2 Hz, aryl-H),
7.86 (4H, d, J=8.4 Hz, aryl-H), 7.34 (2H, d, J=8.8 Hz, aryl-H), 7.11
(2H, d, J=8.4 Hz, aryl-H), 7.05 (2H, d, J=8.4 Hz, aryl-H), 1.61 ppm
(18, s, tert-butyl-H); 13C NMR (125 MHz, (CD3)2CO, 258C): d=31.92,
35.41, 106.65, 113.19, 115.83, 116.47, 116.89, 122.89, 124.38, 128.16,
128.55, 128.87, 129.32,130.95, 131.67, 132.06, 133.27, 133.88,
134.10, 134.93, 135.10, 140.54, 150.08, 151.12, 151.21, 151.40,
152.52, 164.07, 166.98 ppm; UV/Vis (CH2Cl2): lmax =360, 376, 441,
565, 615 nm; MS (MALDI-TOF) m/z: calcd for C68H48N6O6Zn: 1108.3
[M+]; found: 1107.1 [MÀH+]; HRMS (ESI-TOF): m/z: calcd for
C68H48N6O6Zn: 1108.2927 [M+]; found: 1108.2916.
ZnII-1-(4-tert-butyldiphenylsilyloxyphenylethynyl)-5,15-bis(4-tert-
butylphenyl)-10-(N-(4-tert-butyldiphenylsilyloxyphenyl)naphtha-
lene-1,8-dicarboxyimide-4,5-dicarboxyimide)porphyrin (16a):[22]
Et3N (0.92 mL) was added to
a solution of 12a (200 mg,
0.15 mmol), 15 (566 mg, 1.59 mmol), and [Pd(PPh3)4] (9.6 mg,
8.3 mmol) in dry THF (75 mL), and the mixture was heated at reflux
for 20 h. The solvent was removed and the residue was purified by
flash column chromatography on silica gel (CH2Cl2/AcOEt) to
obtain a dark-purple solid(139 mg, 57%). M.p.>3508C (decom-
ZnII-1-(4-hydroxyphenylethynyl)-5,15-bis(4-methoxyphenyl)-10-
(N-(4-hydroxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicar-
boxyimide)porphyrin (2): Deprotected porphyrin 2 was prepared
in a similar manner to 1, but with 16b (20 mg, 13.0 mmol) as the
starting material, to give the product as a dark-green solid (13 mg,
94%). M.p.>4008C; 1H NMR (400 MHz, [D7]DMF, 258C, TMS): d=
10.27 (1H, s, OH), 9.94 (1H, s, OH), 9.88 (2H, d, J=4.4 Hz, b-pyr-
role-H), 9.58 (2H, d, J=4.8 Hz, b-pyrrole-H), 9.01 (2H, d, J=7.6 Hz,
b-pyrrole-H), 8.99–8.94 (4H, m, imide-H), 8.82 (2H, d, J=4.8 Hz, b-
pyrrole-H), 8.17 (2H, d, J=8.4 Hz, aryl-H), 8.07 (2H, d, J=8.4 Hz,
aryl-H), 7.42–7.39 (6H, m, aryl-H), 7.14 (2H, d, J=6.4 Hz, aryl-H),
7.08 (2H, d, J=6.4 Hz, aryl-H), 4.10 ppm (6H, s); 13C NMR
(100 MHz, [D7]DMF, 258C, TMS): d=55.66, 91.38, 97.60, 102.10,
112.60, 114.63, 115,89, 116.01, 116.48, 122.08, 127.36, 127.77,
128.18, 128.82, 129.20, 130.40, 131.05, 131.41, 132.13, 132.64,
133.28, 133.67, 135.11, 135.40, 135.95, 149.61, 150.68, 151.08,
151.78, 158.38, 159.22, 159.78, 163.74, 166.78 ppm; UV/Vis (CH2Cl2):
lmax =223, 296, 359, 374, 440, 566, 616 nm; MS (MALDI-TOF) m/z:
calcd for C62H36N6O8Zn: 1056.2 [M+]; found: 1057.1 [M+H+]; ele-
mental analysis calcd (%) for C62H36N6O8Zn+3H2O (hygroscopic): C
66.94; H 3.81; N 7.55; found: C 66.67; H 3.96: N 7.56.
1
posed); H NMR (400 MHz, CDCl3, 258C, TMS): d=9.70 (2H, d, J=
4.4 Hz, b-pyrrole-H), 8.97–8.91 (6H, m, b-pyrrole-H), 8.92 (4H, s,
imide-H), 8.07 (4H, d, J=8.4 Hz, aryl-H), 7.82–7.73 (14H, m, aryl-H,
and ortho-H of phenylsilyl), 7.47–7.42 (12H, m, meta-H and para-H
of phenylsilyl), 7.09 (2H, d, J=8.4 Hz, aryl-H), 6.99–6.95 (4H, m,
aryl-H), 1.58 (18H, s, tert-butyl-H), 1.17 (9H, s, tert-butyl-H),
1.16 ppm (9H, s, tert-butyl-H); 13C NMR (125 MHz,CDCl3, 258C,
TMS): d=19.52, 26.51, 31.69, 34.87, 120.23, 120.54, 122.57, 123.50,
126.80, 127.02, 127.17, 127.38, 127.50,127.92, 127.94, 129.18,130.09,
130.11, 131.01, 131.63, 132.03, 132.49, 132.53, 132.91, 134.05,
134.30, 135.53, 135.55, 139.19, 148.11,150.36, 150.53, 150.67,
151.89, 156.04, 156.17, 163.19, 165.71 ppm; UV/Vis (CH2Cl2): lmax
=
360, 376, 442, 565, 616 nm; MS (MALDI-TOF): m/z: calcd for
C100H84N6O6Si2Zn 1584.5 [M+]; found: 1585.1 [M+H+]; HRMS (ESI-
TOF): m/z calcd for C100H84N6O6Si2Zn: 1584.5282 [M+]; found:
1584.5289.
ZnII-1-(4-tert-butyldiphenylsilyloxyphenylethynyl)-5,15-bis(4-me-
thoxyphenyl)-10-(N-(4-tert-butyldiphenylsilyloxyphenyl)naphtha-
lene-1,8-dicarboxyimide-4,5-dicarboxyimide)porphyrin
(16b):
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1-(4-tert-Butyldiphenylsilyloxyphenylethynyl)-5,15-bis(4-tert-bu-
tylphenyl)-10-(N-(4-tert-butyldiphenylsilyloxyphenyl)naphtha-
lene-1,8-dicarboxyimide-4, 5-dicarboxyimide)porphyrin (17a):
TFA (3 mL, 0.05 mol) was added to a solution of 16a (103 mg,
0.06 mmol) in CH2Cl2 (100 mL), and the mixture was stirred for 1 h.
It was then neutralized with Na2CO3, the solvent was removed, and
the product was purified by flash chromatography column on
silica gel (CH2Cl2), affording a dark-brown solid (99 mg, 87%):
meta-H and para-H of phenylsilyl), 7.12 (2H, d, J=8.4 Hz, aryl-H),
7.00 (2H, d, J=8.8 Hz, aryl-H), 6.95 (2H, d, J=8.8 Hz, aryl-H), 1.60
(18H, s, tert-butyl-H), 1.17 (9H, s, tert-butyl-H), 1.16 ppm (9H, s,
tert-butyl-H); 13C NMR (125 MHz, (CD3)2CO, 258C): d=19.97, 26.86,
31.89, 35.42, 97.44, 104.02, 117.44, 120.65, 121.17, 123.83, 124.49,
124.64, 128.41, 128.48, 128.57, 128.63, 128.71, 128.87, 128.93,
129.75, 130.06, 130.88, 131.10, 131.18, 131.58, 131.75, 131.91,
132.12132.46, 133.13, 133.30, 133.92, 134.32, 134.62, 134.83,
136.29, 139.55, 144.44, 144.77, 145.88, 151,49, 156.41, 157.23,
163.86, 166.01 ppm; UV/Vis (CH2Cl2): lmax =359, 380, 439, 542,
588 nm; MS (MALDI-TOF): m/z: calcd for C100H84N6O6RhSi2: 1623.5
[MÀI+]; found: 1622.7; HRMS (ESI-TOF) m/z: calcd for
C100H84IN6O6RhSi2: 1750.4091 [M+]; found: 1750.4102; m/z calcd for
1
M.p.>3008C (decomposed); H NMR (400 MHz, CDCl3, 258C, TMS):
d=9.69 (2H, d, J=4.8 Hz, b-pyrrole-H), 9.03–8.96 (4H, m, b-pyr-
role-H), 8.90–8.87 (4H, m, imide-H), 8.84 (2H, d, J=4.8 Hz, b-pyr-
role-H), 8.09 (4H, J=8.4 Hz,aryl-H), 7.82–7.74 (14H,m, aryl-H and
ortho-H of phenylsilyl), 7.49–7.42 (12H, m, meta-H and para-H of
phenylsilyl), 7.12 (2H, d, J=8.8 Hz, aryl-H), 7.00–6.96 (4H, m, aryl-
H), 1.60 (18H, s, tert-butyl-H), 1.17 (9H, s, tert-butyl-H), 1.16 (9H,s,
tert-butyl-H), À2.21 ppm (2H, s, NH); 13C NMR (125 MHz, CDCl3,
258C, TMS): d=19.53, 26.51, 31.65, 34.89, 97.74, 102.24, 110.07,
116.34, 120.31, 120.60, 121.83, 127.06, 127.26, 127.53, 127.60,
127.94, 127.96, 128.07, 129.25, 130.11, 130.14, 131.66, 132.11,
132.51, 133.04, 134.39, 135.53, 135.57, 138.16, 150.76, 156.11,
156.40, 163.12, 165.57 ppm; UV/Vis (CH2Cl2): lmax =379, 437, 532,
579, 572 nm; MS (MALDI-TOF): m/z calcd for C100H86N6O6Si2: 1522.6
[M+]; found: 1524.3 [M+2H+*]; HRMS (ESI-TOF): m/z: calcd for
C100H87N6O6Si2: 1523.6226 [M+H+]; found: 1523.6243.
C
100H84N6O6RhSi2 1623.5046 [MÀI+]; found: 1623.5034.
RhIII-1-(4-tert-butyldiphenylsilyloxyphenylethynyl)-5,15-bis(4-me-
thoxyphenyl)-10-(N-(4-tert-butyldiphenylsilyloxyphenyl)naphtha-
lene-1,8-dicarboxyimide-4,5-dicarboxyimide)porphyrin
iodide
(18b): Rh porphyrin 18b was prepared in a similar manner to 18a,
but with 17b (50 mg, 32.6 mmol) as the starting material, to give
1
a dark-brown solid (56 mg, 97%): M.p.>4008C; H NMR (400 MHz,
CDCl3, 258C, TMS): d=9.69 (2H, d, J=4.8 Hz, b-pyrrole-H), 8.93
(4H, br, b-pyrrole-H), 8.88 (2H, d, J=4.8 Hz, b-pyrrole-H), 8.79 (4H,
br, imide-H), 8.05 (2H, d, J=8.4 Hz, aryl-H), 7.97 (2H, d, J=8.4 Hz,
aryl-H), 7.81–7.75 (10H, m, aryl-H and ortho-H of phenylsilyl), 7.51–
7.41 (12H, m, aryl-H, meta-H and para-H of phenylsilyl), 7.22 (2H, d,
J=8.4 Hz, aryl-H), 7.10 (2H, d, J=8.4 Hz, aryl-H), 6.98 (2H, d, J=
6.4, aryl-H), 6.95 (2H, d, J=6.4, aryl-H), 4.06 (6H, s, methoxy-H),
1.18 (9H, s, tert-butyl-H), 1.16 ppm (9H, s, tert-butyl-H); 13C NMR
(100 MHz, CDCl3, 258C, TMS): d=19.53, 26.53, 55.54, 98.81, 104.
54, 112.28, 116.18, 120.20, 120.42, 123.05, 127.08, 127.38, 127.78,
127.81, 129.09, 129.94, 130.00, 131.33, 131.65, 132.03, 132.40,
132.89, 133.33, 134.23, 134, 51, 135.38, 135.40, 141.45, 143.86,
145.31, 155.92, 156.30, 159.1, 8, 162.79, 164.19, 165.83,
170.81 ppm; UV/Vis (CH2Cl2): lmax =359, 378, 440, 546, 591 nm; MS
(MALDI-TOF): m/z calcd for C94H72N6O8RhSi2: 1571.4 [MÀI+]; found:
1570.6; m/z calcd for C94H72IN6NaO8RhSi2: 1721.3 [M+Na+]; found:
1720.5; elemental analysis calcd (%) for C94H72IN6O8RhSi2 +H2O (hy-
groscopic): C 65.73; H 4,34; I 7.39, N 4.89; found: C 65.66; H 4.54;
N 4.89.
1-(4-tert-Butyldiphenylsilyloxyphenylethynyl)-5,15-bis(4-meth-
oxyphenyl)-10-(N-(4-tert-butyldiphenylsilyloxyphenyl)naphtha-
lene-1,8-dicarboxyimide-4,5-dicarboxyimide)porphyrin
(17b):
Free base porphyrin 17b was prepared in a similar manner to 17a,
but with 16b (10 mg, 65.0 mmol) as the starting material, to give
a dark-brown solid (85 mg, 87%): M.p. 2838C (decomposed);
1H NMR(400 MHz, CDCl3, 258C, TMS): d=9.68 (2H, d, J=4.4 Hz, b-
pyrrole-H), 8.99 (2H, d, J=7.6 Hz, b-pyrrole-H), 8.94 (2H, d, J=
7.6 Hz, b-pyrrole-H), 8.88–8.86 (4H, m, imide-H), 8.81 (2H, d, J=
4.4 Hz, b-pyrrole-H), 8.06 (4H, d, J=7.2 Hz, aryl-H), 7.81–7.77 (10H,
m, aryl-H and ortho-H of phenylsilyl-H), 7.49–7.42 (12H, m, aryl-H
and meta-H and para-H of phenylsilyl), 7.27 (2H, d, J=8.4 Hz, aryl-
H), 7.12 (2H, d, J=6.0 Hz, aryl-H), 7.00 (2H, d, J=6.0 Hz, aryl-H),
6.96 (2H, d, J=8.4 Hz, aryl-H), 4.08 (6H, s, methoxy-H), 1.18 (9H, s,
tert-butyl-H), 1.16 (9H, s, tert-butyl-H), À2.20 ppm (2H, s, NH);
13C NMR (100 MHz, CDCl3, 258C, TMS): d=19.53, 26.52, 55.49,
90.76, 97.72, 102.21, 110.02, 112.27, 116.21, 120.18, 120.45, 121.25,
126.91, 127.16, 128.40, 127.44, 127.78, 127.89, 129.12, 129.94,
131.45, 131, 89, 132.40, 132.41, 132.90, 133.43, 135.38, 135.42,
RhIII-1-(4-hydroxyphenylethynyl)-5,15-bis(4-tert-butylphenyl)-10-
(N-(4-hydroxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-di-
carboxyimide)porphyrin (3): 1m TBAF in THF (40 mL) was added
to a solution of 18a (19 mg, 11.0 mmol) in CH2Cl2 (10 mL) at 08C,
and the mixture was stirred for 1 h. The solvent was then removed
and the residue purified by silica gel column chromatography
(CH2Cl2/MeOH) to give a dark-green solid(14 mg, 96%): M.p.>
3508C; 1H NMR (400 MHz, À(CD3)2CO, 258C): d=9.82 (2H, d, J=
4.8 Hz, b-pyrrole-H), 9.34 (2H, d, J=5.2 Hz, b-pyrrole-H), 8.90–8.99
(6H, m, b-pyrrole-H and imide-H), 8.79 (2H, d, J=5.2 Hz, b-pyrrole-
H), 8.70 (2H, s, OH), 8.18 (2H, d, J=7.2 Hz, aryl-H), 8.09 (2H, d, J=
7.2 Hz, aryl-H), 8.00 (2H, d, J=8.4 Hz, aryl-H), 7.88 (2H, d, J=8.8 Hz,
aryl-H), 7.33 (4H, d, J=8.8 Hz, aryl-H), 7.12 (2H, d, J=8.8 Hz, aryl-
H), 7.04 (4H, d, J=8.8 Hz, aryl-H), 1.61 ppm (18H, s, tert-butyl-H);
13C NMR (125 MHz, (CD3)2CO, 258C): d=31.89, 35.42, 116.43,
116.86, 123.73, 124.49, 124.64, 127.99, 128.30, 128.42, 128.72,
128.82, 129.19, 129.91, 130.87, 131.57, 131.76, 131.94, 132.18,
132.45, 133.78, 134.17, 134.33, 134.63, 134.94, 135.54, 137.21,
139.58, 144.39, 145.86, 151.45, 158.39, 164.00, 166.01 ppm; UV/Vis
(CH2Cl2): lmax =360, 379, 439, 547, 596 nm; MS (MALDI-TOF): m/z
calcd for C68H48N6O6Rh: 1147.3 [MÀI+]; found: 1145.8; m/z calcd for
C68H48N6NaO6Rh: 1297.2 [M+Na+]; found: 1294.8; HRMS (ESI-TOF):
m/z calcd for C68H48IN6NaO6Rh: 1297.1627 [M+Na+]; found:
155.93, 156.25, 159.39, 162.88, 165.34 ppm; UV/Vis (CH2Cl2): lmax
=
378, 437, 534, 579, 673 nm; MS (MALDI-TOF) m/z: calcd for
C94H74N6O8Si2: 1470.5 [M+]; found: 1471.5 [M+H+]; elemental anal-
ysis calcd (%) for C94H74N6O8Si2: C 76.71; H 5.07; N 5.71; found: C
76.81; H 5.32; N 5.75.
RhIII-1-(4-tert-butyldiphenylsilyloxyphenylethynyl)-5,15-bis(4-tert-
butylphenyl)-10-(N-(4-tert-butyldiphenylsilyloxyphenyl)naphtha-
lene-1,8-dicarboxyimide-4,5-dicarboxyimide)porphyrin
iodide
(18a):[23a,b,c] A solution of [Rh(CO)2Cl]2 (16.1 mg, 41 mmol) in dry
CH2Cl2 (2 mL) was added to a solution of 17a (50 mg, 32.8 mmol)
and NaOAc (27 mg, 0.329 mmol) in dry CH2Cl2 (10 mL), and the
mixture was stirred for 4 h. I2 (25.6 mg, 0.1 mmol) was added and
the mixture was stirred for a further 20 h. The mixture was washed
with aq. KI followed by H2O. The solvent was removed and the res-
idue was purified by silica gel column chromatography (CH2Cl2/
AcOEt) to give a dark-brown solid (42 mg, 74%): M.p.>3508C;
1H NMR (400 MHz, CDCl3, 258C, TMS): d=9.72 (2H, d, J=4.8 Hz, b-
pyrrole-H), 9.01–8.91 (6H, m, b-pyrrole-H), 8.87 (4H, s, imide-H),
8.10 (2H, d, J=8.0 Hz, aryl-H), 8.04 (2H, d, J=8.4 Hz, aryl-H), 7.82–
7.71 (14H, m, aryl-H and ortho-H of phenylsilyl), 7.52–7.42 (12H, m,
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1297.1606; m/z calcd for C68H48IN6O6Rh: 1274.1735 [M+]; found:
1274.1712.
Zhong, Z. Liu, Z. Liu, X. Guo, Angew. Chem. 2013, 125, 8828–8832;
Angew. Chem. Int. Ed. 2013, 52, 8666–8670.
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RhIII-1-(4-hydroxyphenylethynyl)-5,15-bis(4-methoxyphenyl)-10-
(N-(4-hydroxyphenyl)naphthalene-1,8-dicarboxyimide-4,5-dicar-
boxyimide)porphyrin (4): Deprotected porphyrin 4 was prepared
in a similar manner to 3, but with 18b (20 mg, 11.0 mmol) as the
starting material, to give a dark-green solid(13 mg, 90%): M.p.>
4008C; 1H NMR (400 MHz, [D7]DMF, 258C, TMS): d=10.31 (1H, s,
OH), 9.94 (1H, s, OH), 9.87 (2H, d, J=5.2 Hz, b-pyrrole-H), 9.65 (2H,
d, J=4.8 Hz, b-pyrrole-H), 9.07 (1H, d, J=7.6 Hz, b- pyrrole-H), 9.00
(1H, d, J=7.6 Hz, b-pyrrole-H),8.97–8.93 (4H, m, imide-H), 8.83 (2H,
d, J=5.2 Hz, b-pyrrole-H), 8.22 (2H, d, J=6.8 Hz, aryl-H), 8.09 (2H,
d, J=8.4 Hz, aryl-H), 7.44–7.40 (6H, m, aryl-H), 7.15 (2H, d, J=
8.4 Hz, aryl-H), 7.07 (2H, d, J=8.4 Hz, aryl-H), 4.12 ppm (6H, s, me-
thoxy-H); 13C NMR (100 MHz, [D7]DMF, 258C, TMS): d=55.70, 89.95,
98.18, 104.11, 112.81, 113.95, 114.19, 116.00, 116.49, 122.98, 127.33,
127.74, 128.07, 128.13, 128.25, 128.34, 128.87, 130.38, 130.96,
131.50, 132.02, 133.25, 133.84, 133.98, 135.42, 135.70, 143.08,
143.95, 145.15, 158.38, 159.46, 160.01, 163.72, 165.83, 166.99 ppm;
UV/Vis (CH2Cl2): lmax =361, 379, 442, 546, 584, 630 nm; MS (MALDI-
TOF): m/z calcd for C62H36N6O8Rh: 1095.2 [MÀI+]; found: 1094.7; m/
z calcd for C62H36IN6NaO8Rh: 1245.1 [M+Na+]; found: 1242.6; ele-
mental analysis calcd (%) for C62H36IN6O8Rh: C 60.90; H 2.97; N
6.87; found: C 55.46; H 3.82; N 6.31.
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Acknowledgements
This study was supported in part by Grants-in-Aid for Scientific
Research (Nos. 23310076 and 24651142) and for Scientific Re-
search on Innovative Areas from the Ministry of Education, Cul-
ture, Science, Sports, and Technology of Japan (Nos. 20111012
and 25110002).Computations were performed at the Research
Center for Computational Science, Okazaki, Japan.
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Received: February 5, 2014
Revised: April 4, 2014
Published online on && &&, 2014
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&
Chem. Eur. J. 2014, 20, 1 – 11
www.chemeurj.org
10
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

Full Paper
FULL PAPER
Molecular diodes: Four types of donor–
acceptor molecules based on perpen-
dicularly connected porphyrin and
naphthalenediimide having different
central metals, zinc(II) and rhodium(III),
have been designed and synthesized to
create donor–acceptor systems with the
desired functionalities for single molec-
ular diodes (see figure). The effects of
central metals on molecular orbitals
provide strong indications that the Rh
porphyrin–imide dyads will show differ-
ent electronic properties to the Zn mol-
ecules.
&
Molecular Devices
M. Handayani, S. Gohda, D. Tanaka,
T. Ogawa*
&& – &&
Design and Synthesis of
Perpendicularly Connected Metal
Porphyrin–Imide Dyads for Two-
Terminal Wired Single Molecular
Diodes
Chem. Eur. J. 2014, 20, 1 – 11
www.chemeurj.org
11
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ