A novel ruthenium(II) tris(bipyridine)-zinc porphyrin-rhenium carbonyl triad: Synthesis and optical properties

Article abstract of DOI:10.1016/j.tet.2006.01.072

A novel ruthenium(II) tris(bipyridine)-zinc porphyrin-rhenium carbonyl triads and its free base porphyrin derivative were synthesized and characterized by ¹H, ¹³C NMR, UV-vis, mass-spectrometry and elemental analysis. The redox poten

Full text of DOI:10.1016/j.tet.2006.01.072

Tetrahedron 62 (2006) 3674–3680
A novel ruthenium(II) tris(bipyridine)–zinc porphyrin–rhenium
carbonyl triad: synthesis and optical properties
a
Xien Liu, Jianhui Liu,
a,
a
*
Jingxi Pan, Ruikui Chen, Yong Na,
a
a
a
Weiming Gao and Licheng Sun
a,b,
*
a
State Key Laboratory of Fine Chemicals, Dalian University of Technology, Zhongshan Road 158-46,
Dalian 116012, People’s Republic of China
b
Department of Chemistry, Royal Institute of Technology (KTH), 10044 Stockholm, Sweden
Received 23 November 2005; revised 18 January 2006; accepted 20 January 2006
Available online 28 February 2006
Abstract—A novel ruthenium(II) tris(bipyridine)–zinc porphyrin–rhenium carbonyl triads and its free base porphyrin derivative were
1
13
synthesized and characterized by H, C NMR, UV–vis, mass-spectrometry and elemental analysis. The redox potentials of the two
compounds were measured and compared to their corresponding reference complexes. The fluorescence and transient absorption spectra of
the two complexes revealed the features of two different pathways for possible photoinduced intramolecular electron transfer or energy
transfer in the triads.
q 2006 Elsevier Ltd. All rights reserved.
1
. Introduction
growing interest for the study of these molecules stems from
their ability to act as efficient sensitizers for energy and
1
1
The preparation of multicomponent photoactive arrays by
logical covalent or noncovalent connection is a rapidly
growing field and an important research area in view of the
following interests: (i) a better understanding of efficient
electron transfer and charge separation in natural photo-
electron transfer. Herein, we sought to prepare a porphyrin-
based triad with Ru(bpy) and [Re(CO) (bpy)L] covalently
X
3
2
3
attached to porphyrin for the studies of electron transfer or
energy transfer in multicomponent systems.
1
2
synthesis; (ii) the construction of the nanometer-scale wires,
3
switches, logic gate, and other components for the
4
2. Results and discussion
2.1. Synthesis
5
development of molecular electronic devices. It has been
known that photoexcitation results in charge transfer from
ion to the bpy ligands in Ru(bpy) X derivatives,
3 2
2C
Ru
3C
K
effectively creating a Ru -(bpy) metal to ligand charge
The procedure for the synthesis of 1 and 1-Zn was depicted in
Scheme 1. The starting porphyrin 2 was synthesized by a
mixed condensation of pyrrole, 4-nitrobenzaldehyde and 4-(t-
6
3C
transfer state. The Ru is an extremely strong oxidant that
could potentially promote facile oxidation of an adjacent
1
2
7
porphyrin via electron transfer. In recent years, a sizable
number of dyads (or larger architectures) comprised of a
butyl)benzaldehyde. The ‘ortho’ orientated 5,10-bis-(4-
nitrophenyl)porphyrin(2)wasseparatedbycolumnchromato-
graphy from other multiple porphyrin products, including
mono, bis (trans), tris and tetrais nitrophenyl-substituted
porphyrins. Gradient elution was used for the multicomponent
separation with silica gel and a dichloromethane/hexane
solvent system consisting initially of CH Cl –Hexane (1/1)
8
porphyrin and a Ru(bpy) complex or Ru(tpy) complex
9
3
2
have been designed and synthesized. The photochemical
properties of a number of such complexes have been
1
0
reviewed. In addition, rhenium-containing complexes
2
2
Re(CO) (bpy)L, in which L is a halide, have been the subject
3
of a large number of studies. In general, the continuously
and gradually ending with 100% of dichloromethane. We did
not collect the trans analogue 5,15-bis-(4-nitrophenyl)por-
phyrin due to its extremely low yield, although TLC analysis
of these mixtures indicated that the trans could be separated.
The following simultaneous reduction of the two nitro groups
Keywords: Porphyrin; Ruthenium; Rhenium; Photophysics; Electron
transfer; Energy transfer.
Corresponding authors. Tel.: C86 411 83702187; fax: C86 411
3702185 (J.L.); (L.S.); e-mail addresses: liujh@dlut.edu.cn;
lichengs@kth.se
*
was carried out in CHCl /HOAc by the usual SnCl /HCl
3
8
2
1
procedure to give amino substituted phenylporphyrin 3 in
3
0040–4020/$ - see front matter q 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2006.01.072

X. Liu et al. / Tetrahedron 62 (2006) 3674–3680
3675
0 0
2 3
Scheme 1. Synthesis of complex 1-Zn. Conditions: (i) SnCl /HCl, CHCl –HOAc reflux, 12 h, 82%; (ii) 4 -methyl-2,2 -bipyridinyl-4-carbonyl chloride,
0
0
CH
2
Cl , reflux, 4 h, 60%; (iii) cis-Ru(4-4 -di-COOEt-2,2 -bpy)
2
2
Cl
2
5 2 2
, HOAc, reflux, 1 h, 32%; (iv) Re(CO) Cl, toluene, reflux 6 h, 98%; (v) Zn(OAc) $2H O,
CHCl
3
–EtOH, rt, 12 h, 94%.
0
0
82% yield. Porphyrin 3 was then reacted with 4 -methyl-2, 2 -
bipyrindyl-4-carbonyl chloride (prepared in situ from 4,4 -
(Fig. 5) was also shown as a comparison. The absorption
spectrum of 1-Zn showed a red-shifted soret band at 428 nm
(S /S transition) with respect to that of 1 (418 nm).
0
0
14
dimethyl-2,2 -bipyridine ) in the presence of Et N to form
3
0
2
compound 4 in 60% yield, where the two amidations occurred
in the same step. For the next transformation to the complex 5,
2
1
1
0
0
.0
1-Zn
0
the acetic acid solutionof 1 equiv of cis-Ru(4, 4 -di-COOEt-2,
15
0
1
2
ensure the regioselectivity. The remaining bipyridine subunit
-bpy) Cl was carefully titrated to porphyrin 4 in order to
2 2
.5
.0
.5
.0
was coordinated to Re by treatment of 5 with Re(CO) Cl in
5
toluene at reflux to give the binuclear product 1 in 98% yield.
The trinuclear target complex 1-Zn was then formed by
stirring the mixture of Zn(OAc) and 1 in chloroform in the
2
presence of a little EtOH at room temperature. All of the
compounds were insoluble in hexane or alcohols but were
easily dissolved in most other organic solvents.
Ru
2
.2. Steady-state absorption spectra
350
400
450
500
550
600
650
700
Wavelength (nm)
The absorption spectra of 1 and 1-Zn were shown in
0
0
Figure 1. The spectrum of Ru(4,4 -di-COOEt-2,2 -bpy) (4-
2
Figure 1. UV–vis absorption spectra of 1, 1-Zn and Ru in CH Cl
2
2
0
0
16
Me-4 -COOH-2,2 -bpy) (PF ) (abbreviated as Ru )
K6
[5!10 M].
6
2

3676
X. Liu et al. / Tetrahedron 62 (2006) 3674–3680
While the two Q bands (S /S transition) exhibited typical
exciting at the ruthenium band (475 nm), the emission
profile of 1-Zn was similar to that of Ru. However, the
intensity of the emission of 1-Zn was found to be 50%
relative to that of Ru. The decrease of emission intensity is
attributed to the quenching of MLCT state of ruthenium
unit by Zn porphyrin via electron or energy transfer.
0
1
pattern of regular metal porphyrins. The shoulders at
75 nm for both spectra of 1 and 1-Zn are mainly from
4
ruthenium moiety, since porphyrins have negligible absorp-
tion in this region. In addition, the metal to ligand charge
transfer (MLCT) transition of ruthenium moieties in all
cases was red shifted (25 nm) relative to the absorption of
3
1
7
Ru(bpy) X , due to the introduction of electron-with-
3
2
2
.4. Transient absorption
drawing substituents in the pyridine rings.
A preliminary time-resolved absorption and emission study of
-Zn was carried out in CH CN solution using a YAG laser
with a 12 ns pulse width and excitation at 532 nm. The
1
2
.3. Emission measurements
3
3
spectrum is characteristic of the porphyrin (p,p*) excited
states with intense absorption at 480 nm (Fig. 3). The (p,p*)
spectrum is also marked by a distinct near-infrared absorption
The emission spectra of 1 and 1-Zn were shown in Figure 2a.
The emission spectrum of complex 1 showed the typical
porphyrin component emission at 656 and 722 nm (0–0 and
3
1
19
peak, which is not found in the (p,p*) spectrum. However,
thereisa significantdifferencebetween the transient spectra of
the 1-Zn and regular zinc porphyrins at 780 nm, in which
transient absorption of the 1-Zn is stronger than that of regular
0
–1 band) upon irradiation at the Q band (552 nm). While the
related peaks in the emission spectrum of 1-Zn were blue-
shifted (0–0 and 0–1 band at 614 and 667 nm, respectively)
upon irradiation at 558 nm, and the emission intensity was
strongly quenched. The emission from Zn porphyrin
component in 1-Zn (F Z0.0005) and porphyrin component
in 1 (F Z0.007) were reduced by 62-fold and 14-fold from
that of zinc tetraphenylporphyrin (F Z0.031) and tetra-
phenylporphyrin (F Z0.10) respectively. Since energy
transfer to the appended ruthenium or rhenium unit is
thermodynamically infeasible, this quenching is mainly
zinc porphyrins. We attribute it to the mixture of the porphyrin
3
(p,p*) excited states and the intraligand charge transfer
transition ( ILCT) from the porphyrin (p) to bpy (p*).
f
3 11b
A
f
lifetimeof783 nswasobtainedfortheexcitedtripletsateofZn
porphyrin by fitting the experimental absorbance decay at
f
f
480 nm, while a lifetime of 489 ns was obtained by fitting the
experimental absorbance decay at 780 nm. The different
lifetime also indicated that the two absorptions at 480 and
9
attributed to electron transfer to the ruthenium unit.
Comparing with a Zn porphyrin–ruthenium complex (F Z
780 nm were attributed to different excited states. A detailed
f
1
.0011), we deduced that rhenium carbonyl unit also played
8
investigation of photoinduced electron transfer and energy
transfer processes occurring in 1-Zn will help us to evaluate
this molecular triad system as a potential light-driven
molecular switch. Femtosecond transient absorption measure-
ments on this complex are in progress.
0
an important role in the electron transfer by quenching of the
emission of zinc porphyrin component in 1-Zn.
The emission spectra of the complex Ru (see Fig. 5)
(
l Z475 nm) and 1-Zn (l Z428, 475, 558 nm) were
ex ex
shown in Figure 2b. We found that the emission profile of
-Zn was identical to that of Zn porphyrin, no matter the
soret band (l Z428 nm) or Q band (l Z558 nm) was
excited. In addition, no contribution from ruthenium or
rhenium moieties could be observed. Thus, the soret band
excitation of Zn porphyrin moiety in 1-Zn did not generate
any sensitized ruthenium or rhenium emission, and energy
2.5. Electrochemistry
1
ex
ex
Redox potentials of the compounds 1, 1-Zn and reference
1
7
2c
compounds Ru, PZnRu and PZnRe (their formulas
were shown in Fig. 5, vide infra) were compiled in Table 1.
The different waves of 1 and 1-Zn could be easily assigned
to their individual components by comparison with the
redox couples of the reference compounds. Compound 1-Zn
had a good reversible characteristic at all redox processes, in
transfer from the S state of Zn porphyrin to ruthenium or
2
rhenium unit therefore could not be significant. When
2.0
1.5
1.0
0.5
0.0
0.25
(b)
(
a)
1
0.20
0.15
0.10
Ru(475nm)
1-Zn(475nm)
1
-Zn(1x10)
0.05
0.00
1-Zn(428nm)
1-Zn(558nm)
600
650
700
750
800
600
650
700
750
Wavelength (nm)
Wavelength (nm)
K6
2 2
Figure 2. (a) Steady-state emission spectra of 1 (lexZ552 nm), 1-Zn (lexZ558 nm) in CH Cl [5!10 M]; (b) steady-state emission spectra of 1-Zn (lexZ
K6
5
2 2
58, 428, 475 nm) and Ru (lexZ475 nm) in CH Cl [5!10 M].

X. Liu et al. / Tetrahedron 62 (2006) 3674–3680
3677
0.3
0.2
0.1
0.0
0.20
0.15
0.10
0.05
0.00
0.15
0.10
0.05
0.00
4
80 nm
780 nm
89 ns
783 ns
4
2500 3000 3500 4000
Time (ns)
2500 3000 3500 4000
Time(ns)
500
600
700
800
Wavelength (nm)
K5
Figure 3. Differential absroption spectrum (visible and near-infrared) obtained upon nanosecond flash photolysis (532 nm) of w1!10 M 1-Zn in
deoxygenated CH CN solutions.
3
Table 1. Redox potentials in CH
2 2
Cl
Oxidation E1/2 (V vs SCE)
Reduction E1/2 (V vs SCE)
C
P/P
C
P
2C
/P
C
Re /Re
2C
2C 3C
Ru /Ru
K
L/L
0
0
K
K
P/P
L /L
Ru
PZnRe
PZnRu
1.66
K0.76
K1.02
K1.06
K1.07
K1.03
K1.14
0.81
0.78
0.83
—
1.22
1.17
1.22
—
1.53
1.68
1.71
1.72
K0.79
K0.76
K0.77
K1.43
1
1
-Zn
1.51
1.47
which there were two one-electron reductions and four
one-electron oxidations (Fig. 4, e.g., 1-Zn). We can see that
(or Ru subunit) excited states. According to the above
analysis, 1-Zn may be suitable for an all-optical switch.
2
C
3C
C
2C
potentials of the Ru /Ru (1.71 V) and Re /Re
1.51 V) couple are more positive than that of the Zn
(
porphyrin constituent (0.83 V). Thus, the complex has the
requisite characteristics to facilitate generation of a
porphyrin p-cation radical upon photoexcitation of the Ru
or Re subunit, when just considering the redox properties.
3
. Conclusion
To investigate intramolecular photoinduced electron or
energy transfer in large light-harvesting arrays or molecular
devices, two new multicomponent arrays based on
porphyrin and ruthenium (or rhenium) bipyridine
complexes were synthesized and characterized. Detailed
This would both quench the fluorescence of the porphyrin
and allow the oxidized porphyrin to quench nearby Re part
1
1-Zn
2
1
0
-1
-2
2
1
0
-1
-2
V vs SCE
V vs SCE
K3
Figure 4. Cyclic voltammogram for complexes 1 and 1-Zn in 10 M of CH Cl /0.1 M TBAPF glassy carbon disc electrode at a scan rate of 50 mV/s and
reported relative to SCE.
2 2 6

3678
X. Liu et al. / Tetrahedron 62 (2006) 3674–3680
N
CO
O
N
N
N
N
N
Re CO
Zn
N
H
Cl
CO
N
CO
O
N
N
N
N
N
Re CO
Zn
N
H
Cl
CO
Figure 5. Schematic formulas of reference compounds studied.
photophysical and electrochemical studies of free-base and
zinc-metalated multicomponents clearly showed that elec-
tronic interactions in each subunit were very weak. In fact,
the absorption spectra and the electrochemical properties
of the two multicomponent arrays can be described by
a superposition of their monomeric subunits. Emission and
transient absorption spectra recorded at room temperature
showed that intramolecular photoinduced electron or energy
transfer might occur.
H , H
1
0
H
0
H8
0
), 8.65 (d, JZ8.0 Hz, 4H, H , H
H H6 ),
0 0 0
1 , 7 ,
2
2 , 5 ,
8.73 (d, JZ4.8 Hz, 2H, pyrrole), 8.78 (s, 2H, pyrrole), 8.91
(s, 2H, pyrrole), 8.96 (d, JZ4.8 Hz, 2H, pyrrole); C NMR
1
3
(CDCl ) d 31.9, 35.1, 117.1, 122.1, 123.9, 134.7, 135.3,
138.8, 147.9, 149.2, 151.1; UV–vis in CH Cl l (nm)Z
3
2
2
max
423.0, 518.0, 554.0, 592.0, 647.0; APCI-MS Positive: [MC
H] (m/zZ817.4). Anal. Calcd for C H N O $0.1CH -
Cl : C, 75.81; H, 5.40; N, 10.18. Found: C, 76.00; H, 5.52;
N, 10.26.
C
5
2
44
6
4
2
2
4.1.2. 5,10-Bis(4-aminophenyl)-15,20-bis(4-tert-butyl-
phenyl)porphyrin (3). SnCl $2H O (915 mg, 4.0 mmol)
4. Experimental
2
2
in concentrated HCl (25 mL) was added to 2 (408 mg,
0.5 mmol) in CHCl –HOAc (1/2) (45 mL). The mixture was
4
.1. General
3
vigorously stirred in a preheated oil bath (65–70 8C) for
30 min, refluxed overnight, and then neutralized with
ammonia solution (25%) to pH 8–9. Chloroform (100 mL)
was added, and the mixture was stirred for 1 h. The organic
phase was separated, and the water phase was extracted with
CHCl3 (2!100 mL). The combined organic layer was
washed once with dilute ammonia solution, three times with
water, and then concentrated to dryness. The residue was
purified by column chromatography (silica gel, CH Cl /
1
7
2c
The reference compounds Ru, PZnRu and PZnRe were
prepared according to the literatures. We showed serial
numbers of compound 1 so that we can easily assign the
1
signal in H NMR (see Fig. 6). All reagents were purchased
from Aldrich, and all solvents were purified according to
standard methods. Pyrrole was freshly distilled before use.
All of the manipulations were performed under N . H NMR
spectra were recorded on a varian 400 spectrometer and
reported in parts per million downfield from TMS.
1
2
2
2
CH CH OHZ200:1) to give the desired porphyrin product
3
2
1
(
309 mg, 82%). MpO300 8C; H NMR (CDCl ) d K2.72
3
4
.1.1. 5,10-Bis(4-nitrophenyl)-15,20-bis(4-tert-butylphe-
(s, br, 2H, –NH), 1.60 (s, 18H, tert-butyl-H), 3.98 (s, br, 4H,
), 7.74 (d,
–NH
JZ8.0 Hz, 4H, H
), 8.14 (d, JZ8.0 Hz, 4H, H , H
0
, H7
1
), 7.03 (d, JZ8.4 Hz, 4H, H
, H
, H11, H11
0
nyl)porphyrin (2). Pyrrole (0.56 mL, 8.0 mmol), 4-nitro-
benzaldehyde (306 mg, 2.0 mmol) and 4-tert-
butylbenzaldehyde (1.04 mL, 6.0 mmol) were added to
CH Cl (1000 mL), which was degassed with N2 for
2
5
6
, H , H12, H12
0
), 7.99 (d, JZ8.0 Hz, 4H,
7
8
H
, H
0
, H5
0
, H6
0
0
, H8
0
),
) d 31.9, 35.1,
113.6, 120.0, 120.6, 123.8, 131.1, 132.8, 134.7, 135.9,
139.5, 146.1, 150.6; UV–vis in CH Cl max (nm)Z421.0,
517.0, 555.0, 591.0, 650.0; APCI-MS Positive: [MCH]
(m/zZ757.5). Anal. Calcd for C52 $0.75CH CH OH:
2
2
1
1
3
8.86–8.91 (m, 8H, pyrrole); C NMR (CDCl
2
2
3
3
3
2
0 min. After the mixture was stirred under N for a further
2
0 min, a BF /etherate solution (1.0 mL, 2 M in CH Cl ,
3
.0 mmol) was added dropwise. The reaction mixture was
l
2
2
2
2
C
stirred overnight at room temperature. 2,3-Dichloro-5,6-
dicyanobenzoquinone (DDQ) (1.82 g, 8.0 mmol) was added
to the red-brown solution, and the resulting black mixture
H
48
N
6
3
2
C, 81.18; H, 6.69; N, 10.62. Found: C, 81.58; H, 6.83; N,
10.21.
was refluxed for 2 h. Et N (1.12 mL, 8.0 mmol) was added
3
to the mixture, and the solution was concentrated to dryness
under reduced pressure. The residue was purified by column
chromatography (silica gel, hexane/CH Cl Z50:50) to give
4.1.3. Porphyrin-(NHCO-bpy) (4). A mixture of
2
4-carboxy-4 -methyl-2,2 -bipyridine (350 mg, 1.636 mmol)
0
and SOCl (20 mL) was refluxed for 2 h. After removal of the
0
2
2
2
the desired porphyrin product (196 mg, 12%). MpO300 8C;
excess SOCl by distillation under reduced pressure, the acid
2
1
H NMR (CDCl ) d 2.78 (s, br, 2H, –NH), 1.61 (s, 18H, tert-
0
chloride product was obtained and dried in vacuum at 70 8C
for 1 h. Then dry CH Cl (12 mL) was added and the mixture
was stirred for 5 min at 50 8C. The resulting light yellow
3
butyl-H), 7.78 (d, JZ8.0 Hz, 4H, H , H , H , H
), 8.14 (d,
7
8
12
12
2
2
JZ8.0 Hz, 4H, H , H , H , H ), 8.40 (d, JZ8.0 Hz, 4H,
0
11
5
6
11

X. Liu et al. / Tetrahedron 62 (2006) 3674–3680
3679
8
6
7
COOEt
1
4'
17'
5
1
1
5'
8'
1
3'
16'
19'
9
4
N
N
10
3
13
O
12
11
2
1
NH
N
N
Ru
N
COOEt
N
2
1'
H
15
1
4
1
20'
2
N
HN
18
N
N
2'
1'
12' 11'
10'
3'
20
COOEt
1
7
9
'
4'
1
6
19
5'
7'
EtOOC
6
'
'
8
HN
O
1
3'' 13'''
1
4'''
1
4''
1
N
N
5''
1
5'''
OC
Re
Cl
OC
CO
1
Figure 6. Serial numbers of the complex 1.
solution was added dropwise to the CH Cl solution (30 mL)
2
of 3 (268 mg, 0.35 mmol) in which two drops of Et N were
3
added. White smoke was observed in the reaction flask. The
mixture was refluxed overnight, and washed with 5% of
aqueous ammonia solution and then water. After removing the
solvent, the residue was dissolved in CHCl (20 mL) and
3
CH CN (200 mL) was added dropwise. Precipitate was
3
formed by slowly evaporating CHCl under vacuum. The
3
d K2.81 (s, br, 2H, –NH), 1.42–1.46 (m, 12H,
–COOCH CH ), 1.53 (s, 18H, tert-butyl), 2.48 (s, 3H,
bpy–CH ), 2.63 (s, 3H, Ru unit-bpy-CH ), 4.48–4.50 (m,
2
2
3
3
3
8H, –COOCH CH ), 7.29–7.31 (m, 1H, H ), 7.35–7.37
0
14
2
3
(m, 1H, H15
(m, 4H, H , H , H , H
0
), 7.58 (d, JZ5.2 Hz, 1H, H14000), 7.64–7.70
0
), 7.84–7.88 (m, 4H, H , H ,
0
7
8
12
12
5
6
H , H
11
0
), 7.92–8.16 (m, 20H, H , H
1
0
, H , H
0
, H5
0
, H
6 ,
, H , H , H ,
11
1
2
2
H7
0
, H8
0
, H , H 00, H , H 00 H , H
0
0
14
14
15
15 ,
17
17 18 18 20
desiredproductwasobtainedaftercolumnchromatographyon
silica gel with a mixture of CH Cl –MeOH (95/5) as eluent to
H20
H13
0
, H , H
21 21
0), 8.32 (s, 1H, H15000), 8.59–8.61 (m, 1H,
0
), 8.65–8.89 (m, 9H, pyrrole-H, H1300), 8.95–8.97 (m,
, H , H ),
2
2
1
give purple solid (242 mg, 60%). MpO250 8C; H NMR
CDCl ) K2.75 (s, br, 2H –NH), 1.58 (s, 18H, tert-butyl-H),
1H, H13000), 9.04–9.12 (m, 5H, H , H , H
0
0
19
13
16
16
19
(
9.43 (s, 1H, amide-H), 9.51 (s, 1H, Ru unit-amide-H);
UV–vis in acetonitrile lmax (nm)Z306.0, 418.0, 514.0,
551.0, 594.0, 646; IR (KBr, nCO): 558, 844, 1731,
3422 cm ; API-ES-MS m/z: [MKPF ] 1996.3, [MK
6
2
2PF6] 925.0. Anal. Calcd for C108H F N O P -
96 12 14 10 2
3
2
7
2
.48 (s, 6H, bpy–CH ), 7.21 (d, JZ4.8 Hz, 2H, H14
0, H14000),
3
.71 (d, JZ8.0 Hz, 4H, H , H , H , H ), 7.96 (d, JZ3.2 Hz,
0
5
6
11 11
K1
C
H, H , H 00), 8.05(d, JZ8.4 Hz, 4H, H , H H , H
0
), 8.09
1
4
14
7
8, 12 12
C
(d, JZ8.0 Hz, 4H, H , H2
H , H
2
0
, H5
), 8.34 (s, 2H, H13
, H15000), 8.68 (s, 2H, amide–H), 8.85–8.86 (m, 8H,
0
, H6
0
), 8.20 (d, JZ8.4 Hz, 4H,
2
0
, H7
0
, H8
0
0
, H13000), 8.59 (d, JZ5.2 Hz,
Ru$1.8HPF : C, 53.96; H, 4.10; N, 8.16. Found: C,
6
53.99; H, 3.95; N, 7.98.
1
1
H, H15
0
1
3
pyrrole-H), 8.88–8.91 (m, 4H, H , H 00, H , H 00); C NMR
1
3
13
15 15
(
CDCl ) d 21.5, 31.9, 35.1, 117.6, 118.8, 119.2, 120.6, 121.7,
3
4.1.5. Porphyrin-(NHCO-bpy) -Ru[(bpy)(COOEt) ] -
2
2 2
1
1
22.3, 122.6, 123.5, 125.7, 131.5, 133.3, 134.6, 135.4, 137.4,
39.2, 143.3, 149.1, 150.6, 155.1, 156.9, 163.6; UV–vis in
(Re(CO) Cl)[PF ] (1). A mixture of 5 (100 mg,
3 6 2
0.046 mmol) and Re(CO) Cl (25 mg, 0.07 mmol) in toluene
5
CH Cl l (nm)Z421.0, 518.0, 554.0, 594.0, 647.0; APCI-
(90 mL) was refluxed for 6 h under N in the dark. After
2
2
2
max
C
MS Positive: [MCH] (m/zZ1149.5). Anal. Calcd for
C H N O $0.4CH Cl : C, 77.54; H, 5.52; N, 11.84.
Found: C, 77.82; H, 5.74; N, 12.00.
removing the solvent, the product was loaded on column of
silica gel with a mixture of MeOH–CH Cl (1/100) as
eluent. The desired product was obtained as a yellow-brown
7
6
64 10
2
2
2
2
2
1
solid (112 mg, 98%). MpO250 8C; H NMR (CD CN) d
3
4.1.4. Porphyrin-(NHCO-bpy) -Ru[(bpy)(COOEt) ] [-
PF6]2 (5). A mixture of 4 (100 mg, 0.087 mmol) and
K2.81 (s, br, 2H, –NH), 1.40–1.44 (m, 12H, –COOCH2-
CH ), 1.56 (s, 9H, tert-butyl), 1.58 (s, 9H, tert-butyl), 2.61
2
2 2
3
Ru[bpy(COOEt) ] Cl (134 mg, 0.174 mmol) in acetic acid
2
(s, 3H, bpy–CH ), 2.63 (s, 3H, Ru-bpy–CH ), 4.45–4.48 (m,
3
2
2
3
(
30 mL) was refluxed for 1 h under N in the dark. After
2
8H, –COOCH CH ), 7.34 (d, JZ5.6 Hz, 1H, H ), 7.53 (d,
0
2
3
14
removing the solvent, the product was loaded on column
of silica gel with a mixture of CH Cl –MeOH (10/1) as
eluent, and the anion was exchanged with NH PF . The
product was obtained as a red-brown solid, which was the
desired 5 (60 mg, 32%). MpO250 8C; H NMR (CD CN)
JZ6.8 Hz, 2H, H15
0
, H14000), 7.78–7.85 (m, 6H, H , H
0
H ,
, H ,
7
7 ,
8
H8
H18
H2 , H , H
H15000), 8.71 (s, 1H, H13
0
H , H
0
), 7.89–8.01 (m, 10H, H , H , H , H
), 8.07–8.28 (m, 12H, H , H
1
0 0 0 H1400, H1500), 8.55 (s, 1H,
0
2
2
12
12
14
15
17
17
18
0
, H , H
0
, H , H
0
0
, H2,
4
6
20
20
21
21
1
0
H , H H , H
5 6 6 , 11 11 ,
5
1
0
), 8.85–8.91 (m, 8H, Pyrrole-H), 8.95
3

3680
X. Liu et al. / Tetrahedron 62 (2006) 3674–3680
(
s, 1H, H13000), 9.07–9.13 (m, 5H, H , H , H
0
, H , H ),
0
19
3. (a) Gilat, S. L.; Kawai, S. M.; Lehn, J. M. Chem. Eur. J. 1995,
1, 275–287. (b) Jose, D. A.; Shukla, A. D.; Kumar, D. K.;
Ganguly, B.; Das, A.; Ramakrishna, G.; Palit, D. K.; Ghosh,
H. N. Inorg. Chem. 2005, 44, 2414–2425.
13
16
16
19
9
.25 (d, 1H, JZ5.2 Hz, H1300), 9.58 (s, br, 1H, amide-H),
9.64 (s, br, 1H, amide-H); UV–vis in acetonitrile lmax
(
nCO): 558, 844, 1729, 1917, 2022, 3398 cm ; API-ES-MS
nm)Z275.0, 418.0, 515.0, 551.0, 592.0, 646; IR (KBr,
K1
4. Wasielewski, M. R.; O’Neil, M. P.; Gosztola, D.;
Niemczyk, M. P.; Svec, W. A. Pure Appl. Chem. 1992,
64, 1319–1325.
C
2C
m/z: [MKPF ] 2300.5, [MK2PF ] 1078.9. Anal. Calcd
6
6
for C111H ClF N O P ReRu$2CH Cl : C, 51.87; H,
2
96
12 14 13
2
2
3
.85; N, 7.49. Found: C, 51.97; H, 3.79; N, 7.29.
5. (a) Molecular Electronic Devices; Carter, F. L., Siatowski,
R. E., Woltjen, H., Eds.; North-Holland: Amsterdam, 1988. (b)
Balzani, V.; Scandola, F. Supramolecular Photochemistry;
Horwood: Chichester, UK, 1991; Chapter 12. (c) Holten, D.;
Bocian, D. F.; Lindsey, J. S. Acc. Chem. Res. 2002, 35, 57–69.
6. Meyer, T. J. Acc. Chem. Res. 1989, 22, 163–170.
7. Wacholtz, W. F.; Auerbach, R. A.; Schmehl, R. H. Inorg.
Chem. 1986, 25, 227–234.
4
.1.6.
Zn-Porphyrin-(NHCO-bpy)2-
(1-Zn).
Zn(OAc) $2H O (20 mg, 0.100 mmol) in ethanol (2 mL)
Ru[(bpy)(COOEt) ] (Re(CO) Cl)[PF ]
6 2
2
2
3
2
2
was added to 1 (61 mg, 0.025 mmol) in chloroform
15 mL), and stirred at room temperature overnight under
N in the dark. This mixture was washed with water and
(
2
extracted with CHCl . The combined organic phase was
3
8. (a) Toma, H. E.; Araki, K. Coord. Chem. Rev. 2000, 196,
307–329. (b) Chichak, K.; Branda, N. R. Chem. Commun.
2000, 1211–1212. (c) Lintuluoto, J. M.; Borovkov, V. V.;
Inoue, Y. Tetrahedron Lett. 2000, 41, 4781–4786. (d)
Allwood, J. L.; Burrell, A. K.; Officer, D. L.; Scott, S. M.;
Wild, K. Y.; Gordon, K. C. Chem. Commun. 2000,
747–748. (e) Harriman, A.; Hissler, M.; Trompette, O.;
Ziessel, R. J. Am. Chem. Soc. 1999, 121, 2516–2525. (f)
Hamachi, I.; Tanaka, S.; Tsukiji, S.; Shinkai, S.; Oishi, S.
Inorg. Chem. 1998, 37, 4380–4388. (g) Sessler, J. L.;
Capuano, V. L.; Burrell, A. K. Inorg. Chim. Acta 1993,
204, 93–101. (h) Hamilton, A. D.; Rubin, H.-D.; Bocarsly,
A. B. J. Am. Chem. Soc. 1984, 106, 7255–7257.
evaporated to dryness and purified by CH Cl –MeOH (10/
2
2
1
). The desired product was obtained as a red-brown solid
1
(
58 mg, 94%). MpO250 8C; H NMR (CD CN) d 1.41–
3
1
.45 (m, 12H, –COOCH CH ), 1.57 (s, 9H, tert-butyl), 1.58
2 3
(
s, 9H, tert-butyl), 2.60 (s, 3H, bpy–CH ), 2.62 (s, 3H, Ru-
3
bpy–CH ), 4.46–4.50 (m, 8H, –COOCH CH ), 7.36 (d, JZ
3
2
3
7
.6 Hz, 1H, H14
0
), 7.55 (d, JZ5.2 Hz, 2H, H15
0
, H14000), 7.81–
H , H ), 7.92–8.02 (m, 10H,
7
H , H , H , H
.87 (m, 6H, H , H
0
H , H
, H , H
0
0
7
7 ,
8
8
12
12
0
0
, H , H
20
0
, H , H ), 8.03–
0
21
1
4
15
17
17
18
18
20
21
8
.29 (m, 12H, H , H
1
0
, H , H
2
0
, H , H
5
0
H , H
6
0
H , H 00
1
2
5
6 , 11 11 ,
H1400, H1500), 8.56 (s, 1H, H15000), 8.73 (s, 1H, H13
m, 8H, pyrrole-H), 8.98 (s, 1H, H13000), 9.06–9.13 (m, 5H,
H , H , H , H , H
), 9.27 (d, 1H, JZ5.2 Hz, H1300),
0
), 8.87–8.95
(
0
0
19
1
3
16
16
19
9. (a) Collin, J.-P.; Dalbavie, J.-O.; Sauvage, J.-P.; Flamigni,
L.; Armaroli, N.; Balzani, V.; Barigelletti, F.; Montanari, I.
Bull. Chem. Soc. Fr. 1996, 133, 749–756. (b) Harriman, A.;
Odobel, F.; Sauvage, J.-P. J. Am. Chem. Soc. 1995, 117,
9461–9472.
9
.60 (s, br, 1H, amide-H), 9.65 (s, br, 1H, amide-H); UV–vis
in acetonitrile lmax (nm)Z308.0, 428.0, 563.0, 605.0; API-
C 2C
ES-MS m/z: [MKPF ] 1904.7, [MK2PF ] , 1108.3.
6
6
Anal. Calcd for C111H Cl F N O P ReRuZn$1.5CH -
94
12 14 13
2
2
Cl : C, 51.23; H, 3.71; N, 7.43. Found: C, 51.61; H, 3.65; N,
2
10. Flamigni, L.; Barigelletti, F.; Armaroli, N.; Collin, J.-P.;
Dixon, I. M.; Sauvage, J.-P.; Williams, J. A. G. Coord. Chem.
Rev. 1999, 190–192, 671–682.
7
.10.
1
1. (a) Gabrielsson, A.; Hartl, F.; Smith, J. R. L.; Perutz, R. N.
Chem. Commun. 2002, 950–951. (b) Guerzo, A. D.; Leroy,
S.; Fages, F.; Schmehl, R. H. Inorg. Chem. 2002, 41,
Acknowledgements
This work was supported by National Natural Science
Foundation of China (20128005), the Ministry of Science
and Technology, the Ministry of Education
(2001CCA02500), the Swedish Energy Agency and the
Swedish Research Council.
3
59–366. (c) Johnson, F. P. A.; George, M. W.; Hartl, F.;
Turner, J. J. Organometallics 1996, 15, 3374–3387. (d)
Yoon, D. I.; Berg-Brennan, C. A.; Lu, H.; Hupp, J. T. Inorg.
Chem. 1992, 31, 3192–3194.
1
2. Lindsey, J. S.; Schreiman, I. C.; Hsu, H. C.; Kearney,
P. C.; Marguerettaz, A. M. J. Org. Chem. 1987, 52,
8
27–836.
1
1
3. Hunter, C. A.; Sarson, L. D. Angew. Chem., Int. Ed. Engl.
1994, 33, 2313–2316.
References and notes
. (a) The Reaction Center of Photosynthetic Bacteria; Michel-
4. McCafferty, D. G.; Bishop, B. M.; Wall, C. G.; Hughes, S. G.;
Mecklenberg, S. L.; Meyer, T. J.; Erickson, B. W. Tetrahedron
1995, 51, 1093–1106.
1
Beyerle, M.-E., Ed.; Springer: Berlin, 1995. (b) Barber, J.;
Anderson, B. Nature 1994, 370, 31–33.
15. Kormann, C.; Bahnemann, D. W.; Hoffmann, M. R. J. Phys.
Chem. 1988, 92, 5196–5201.
16. Pan, J.; Xu, Y.; Benk o¨ , G.; Feyziyev, Y.; Styring, S.; Sun, L.;
2
. (a) Sauvage, J.-P.; Collin, J.-P.; Chambron, J.-C.; Guillerez,
S.; Coudret, C.; Balzani, V.; Barigelletti, F.; De Cola, L.;
Flamigni, L. Chem. Rev. 1994, 94, 993–1019. (b) Balzani,
V.; Juris, A.; Venturi, M.; Campagna, S.; Serroni, S. Chem.
Rev. 1996, 96, 759–833. (c) Grosshenny, V.; Harriman, A.;
Hissler, M.; Ziessel, R. J. Chem. Soc., Faraday Trans.
˚
Akermark, B.; Polivka, T.; Sundstr o¨ m, V. J. Phys. Chem. B 2004,
108, 12904–12910.
17. Graff, J. L.; Sobieralski, T. J.; Wrighton, M. S.; Geoffroy, G. L.
J. Am. Chem. Soc. 1982, 104, 7526–7533.
18. Liu, X.; Liu, J.; Jin, K.; Yang, X.; Peng, Q.; Sun, L.
Tetrahedron 2005, 61, 5655–5662.
1
996, 92, 2223–2238. (d) Benniston, A. C.; Chapman,
G. M.; Harriman, A.; Mehrabi, M. J. Phys. Chem. A 2004,
08, 9026–9036. (e) Dixon, I. M.; Collin, J. P.; Sauvage,
J. P.; Flamigni, L. Inorg. Chem. 2001, 40, 5507–5517.
1
19. Rodriguez, J.; Kirmaier, C.; Holten, D. J. Am. Chem. Soc.
1989, 111, 6500–6506.