Coherently aligned porphyrin-appended polynorbornenes

Article abstract of DOI:10.1002/chem.200900195

Six different kinds of coherently aligned porphyrin-appended polynorbornenes derived from 5,6-endo-fused N-arylpyrrolidenonorbornenes have been synthesized. P-P interactions between the pendant groups are essential for dictating the photophysi-cal propert

Full text of DOI:10.1002/chem.200900195

FULL PAPER
DOI: 10.1002/chem.200900195
Coherently Aligned Porphyrin-Appended Polynorbornenes
Hsian-Wen Wang,[a] Zhi-Chang Liu,[b] Chih-Hsien Chen,[a] Tsong-Shin Lim,[c]
Wunshain Fann†,[d] Chih-Gang Chao,[a] Jian-Yuan Yu,[a] Shern-Long Lee,[a]
Chun-hsien Chen,[a] Shou-Ling Huang,[a] and Tien-Yau Luh*[a, b]
Dedicated to Professor Armin de Meijere on the occasion of his 70th birthday
Abstract: Six different kinds of coher-
ently aligned porphyrin-appended poly-
norbornenes derived from 5,6-endo-
have alkyl-substituted porphyrin pen-
AHCTUNGTRENNdGUN ant groups, suggests strong exciton
coupling between chromophores. No
splitting of the Soret band is observed
for polymers 2d–f, which have tetraaryl
substituents on the porphyrin moiety.
Significant fluorescence quenching is
found in polymers 2a–e, whereas only
slightly reduced quantum yield is ob-
served for 2 f. Time-resolved fluores-
cence measurements also indicate a
similar trend. The AFM image of 2d
on graphite shows aggregation to form
a two-dimensional, ordered pattern.
fused
N-arylpyrrolidenonorbornenes
have been synthesized. p–p interac-
tions between the pendant groups are
essential for dictating the photophysi-
cal properties of the polymers and the
mechanism for the stereoselective for-
mation of polymers. Splitting of the
Soret band of polymers 2a–c, which
Keywords: Arylpyrrolidenes
photophysics polynorbornene
·
·
·
porphyrinoids · ring-opening poly-
merization
Introduction
eties and pigments within protein matrices, in which efficient
capture of solar energy and electron transfer take place.[1]
Relative orientations and distances between chromophores
may be crucial for these important, efficient, and ultrafast
photoinduced processes. Numerous model systems with dif-
ferent cofacial alignments of porphyrin derivatives have
been designed to mimic this important biological process.[2]
For example, cofacial bisporphyrin dyads,[2f] multiple deck
oligoporphyrins,[3] multiporphyrinic dendrimers,[4] and por-
phyrin-appended macromolecules[5] have been extensively
examined for through-space singlet and/or triplet energy
transfers. A molecular assembly based on derivatized poly-
styrenes with pendant polypyridine complexes of RuII has
been used to mimic both the light-harvesting and energy-
conversion steps of photosynthesis.[6] More rigid polynorbor-
nenes with electroactive pendants have also been employed
for photoinduced electron transfer investigations.[7] The use
of tetraphenylporphyrin pendant groups in a norbornene-
based block copolymer has been briefly explored for a possi-
ble molecular switch device.[8] It has recently been shown
that polynorbornenes with N-aryl-substituted 5,6-endo-fused
pyrrolidine, obtained by ring-opening metathesis polymeri-
zation (ROMP) of the corresponding norbornene monomers
catalyzed by the Grubbs I catalyst, may have homogeneous
stereochemistry in which all pendants align coherently in
The photosynthetic system of purple bacteria has been
shown to contain a supramolecular array of chlorophyll moi-
[a] H.-W. Wang, Dr. C.-H. Chen, C.-G. Chao, J.-Y. Yu, S.-L. Lee,
Prof. C.-h. Chen, S.-L. Huang, Prof. T.-Y. Luh
Department of Chemistry
National Taiwan University
Taipei, 106 (Taiwan)
Fax : (+886)2-2364-4971
E-mail: tyluh@ntu.edu.tw
[b] Z.-C. Liu, Prof. T.-Y. Luh
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
354 Fenglin Lu, Shanghai 200032 (China)
[c] Prof. T.-S. Lim
Department of Physics
Tung Hai University
Taichung, 407 (Taiwan)
[d] Prof. W. Fann
Institute of Atomic and Molecular Science
Academia Sinica
Taipei, 106 (Taiwan)
[†] Deceased.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200900195.
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the same direction.[9] In addition, the double bonds in these
polymers were predominantly, if not exclusively, trans. The
space occupied by each of the monomeric units in these
polymers is about 5.5 ꢁ.[9] This strategy has been employed
for the design and synthesis of double-stranded polybisnor-
bornenes.[10] Electrochemical and magnetic investigations of
these double-stranded polymers showed that there are
strong interactions between the ferrocene linkers due to
their close proximity.[11] It is envisaged that the incorpora-
tion of porphyrin pendants in polynorbornenes would pro-
vide an intriguing model in which all porphyrin moieties
would be aligned in a similar direction and that interactions
between these pendant macrocyclic aromatic rings might
offer intriguing photophysical behavior. Herein we wish to
report the synthesis and photophysical properties of porphy-
rin-appended polynorbornenes.
Results and Discussion
Synthesis: The porphyrin moieties in norbornene monomers
1a–f were prepared by using the Lindsey procedure
(Schemes 1 and 2) and the details are described in the Ex-
perimental Section.[12] Polymerization of 1a–f in the pres-
ence of the Grubbs I catalyst afforded the corresponding
dark purple polymers 2a–f (Scheme 2) in good yields. The
Scheme 2. Synthesis of 1 and 2 (n/a=no linker). a) (COCl)2; b) Cs2CO3,
BrCH2CO2Bu; c) TFA; d) 8, NEt3, DMAP (4-dimethylaminopyridine);
e) 9, NEt3, DMAP; f) Compound 10, then LAH (lithiumaluminum hy-
dride); g) ZnACTHNUTRGNEUNG(OAc)2·2H2O; h) [(Cy3)2Cl2Ru=CHPh].
13C NMR spectra of 2a–f were similar to those of corre-
sponding monomers 1a–g and consistent with the structures.
1
1H NMR spectra: The partial H NMR spectra of the aro-
matic regions of 2a–f are compared with those of 1a–f in
Figure 1. Besides severe line broadening,[13] the signals for
the protons on porphyrin moieties in 2a–f were shifted up-
field compared with those of the corresponding monomers
1a–c due to anisotropic shielding by the neighboring por-
phyrin moieties. Similar behavior was found in cofacial mul-
tiple deck oligoporphyrins[3] and related systems.[14] These
results suggest that the neighboring porphyrin pendants in
2a–c may be in close proximity and, therefore, these chro-
mophores may align coherently in a similar direction.
As can be seen from Figure 1, the signals for the b pro-
tons on the porphyrin rings in 2a–c were more affected than
those in 2d–f. These results suggest that the neighboring
porphyrin chromophores would be in closer proximal rela-
tionships for 2a–c than those for 2d–f. It is worth noting
that polymers 2d–f have aryl substituents at the other meso-
positions of the porphyrin skeleton whereas 2a–c have alkyl
Scheme 1. Synthesis of substituted porphyrins 5: a) BF3·OEt2 or TFA (tri-
fluoroacetic acid), then DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoqui-
none), then NEt3, RT; b) DIBAL-H (diisobutylaluminum hydride);
c) SnCl2·2H2O, concd HCl; d) ZnACHTUNTRGNEUNG(OAc)2·2H2O; e) H2, Pd/C, then
DIBAL-H.
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Porphyrin-Appended Polynorbornenes
FULL PAPER
Figure 2. Top: TMAFM image of 2d on highly ordered pyrolytic graphite.
Bottom: The section profile of the dash line showing the spacing of
about 5 nm. Imaging conditions: 257 kHz for the drive frequency of the
tip.
double-stranded polybisnorbornenes[10,11] and is ascribed to
intermolecular interactions, such as p–p stacking between
terminal groups along the longitudinal dimension and van
der Waal interactions between the polymeric backbones and
pendant groups in the horizontal direction. The aligned
stripes have a uniform width of around 5 nm. The uniformi-
ty and the dimension suggest the porphyrin pendants are co-
facially attached to the bisnorbornene backbone.
Photophysical properties: The absorption spectra of 1a–f
and 2a–f in CH2Cl2 are shown in Figure 3 and selected pho-
tophysical properties are summarized in Table 1. It is worth
noting that the Soret band of polymers 2a–c split into two
bands, which indicates that there may be significant exciton
coupling between neighboring porphyrin chromophores
even though the distance between these neighboring pend-
ant moieties would be around 5.5 ꢁ. In addition, the relative
intensities of the shorter wavelength absorption versus the
longer wavelength absorption in the split Soret band de-
creased as the number of methylene moieties in the linkers
of 2a–c increased. The incorporation of methylene groups in
the pendants may increase its flexibility and the exciton cou-
pling between meighboring chromophores may be affected.
It is known that intramolecular interactions between two
porphyrin moieties leading to the splitting of the Soret band
may depend on the distance and dihedral angle between the
two chromophores.[8,17,18] In general, the exciton interaction
between two porphyrins is relatively weak if the face-to-face
distance between porphyrins in cofacial bisporphyrins is
more than 5 ꢁ.[19] The 5.5 ꢁ distance between the cofacial
porphyrin chromophores in 2a–c would be rather large to
exhibit exciton coupling.[20] Slight flexibility in the linkers of
2a–c might result in a closer face-to-face distance between
the neighboring porphyrin moieties or adjust the dihedral
angle between two transition dipoles and lead to exciton
coupling.
Figure 1. Partial 1H NMR spectra (aromatic region) of 1a–f and 2a–f in
CDCl3.
substituents at the same positions. Tetraphenylporphyrin is
known to be nonplanar.[15] As mentioned in the Introduction
Section, the spacing occupied by each of the monomeric
units in 2 would be around 5.5 ꢁ. Steric repulsion between
neighboring pendant groups in 2d–f might be expected if
they were in more eclipsed conformations. It seems likely
that the porphyrin pendants in 2d–f might be more stag-
gered than those in 2a–c. These characteristics might also be
reflected in their photophysical properties as discussed
below.
Tapping-mode atomic force microscopy (TMAFM) images:
TMAFM was carried out to morphologically assess the cofa-
cial stacking of the appended porphyrins. To facilitate the
imaging, the sample was subjected to shear treatment[16] im-
mediately after it was dropcast on the freshly cleaved sur-
face of highly ordered pyrolytic graphite. A typical image of
polymer 2d, which is a prototype for this series of polynor-
bornenes, is displayed in Figure 2 and shows a long-range or-
dered pattern with stripes significantly longer than the ap-
parent length of 2d. Such an assembly is common for
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T.-Y. Luh et al.
Figure 3. Absorption spectra of 1a–f and 2a–f in CH2Cl2.
Table 1. UV/Vis absorption and fluorescent spectral data for 1 and 2 in CH2Cl2.
Mn (PDI)
Absorption
Soret band lmax [nm]
Emission
lmax [nm]
Lifetime
t [ps]
[a]
[b]
Q-band lmax[a] [nm]
Ff[c]
1a
2a
1b
2b
1c
2c
1d
2d
1e
2e
1 f
2 f
1164
18900 (1.08)
1177
17000 (1.19)
1206
15300 (1.13)
1193
10600 (1.38)
1313
51400 (1.58)
1372
420 (3.39)
407 (1.71), 420 (1.51)
420 (3.26)
407 (1.55), 420 (1.94)
419 (3.21)
407 (1.78), 420 (1.17)
423 (2.57)
426 (1.55)
423 (4.85)
423 (3.31)
422 (5.14)
554 (0.17), 593 (0.07)
558 (0.10), 600 (0.05)
554 (0.14), 593 (0.06)
557 (0.12), 596 (0.06)
554 (0.14), 593 (0.06)
557 (0.10), 597 (0.05)
553 (0.19), 596 (0.12)
557 (0.12), 600 (0.07)
550 (0.22), 589 (0.08)
552 (0.21), 592 (0.08)
550 (0.26), 590 (0.16)
551 (0.18), 592 (0.06)
599
614
600
605
600
603
619
624
602
610
601
604
0.036
0.004
0.036
0.007
0.034
0.008
0.041
0.010
0.040
0.025
0.031
0.027
1450
158 (73%), 1450
1420
182 (72%), 1420 (28%)
1470
190 (74%), 1470 (26%)
1360
97 (60%), 1370 (40%)
1340
228 (72%), 1350 (28%)
1360
ACHTUNGTRENNUNG( 27%)
9500 (1.16)
423 (3.66)
310 (26%), 1360 (74%)
[a] The molar extinction coefficient (105 mÀ1 cmÀ1) based on the molecular weight of the monomeric unit is shown in parentheses. [b] Excitation at lmax
around 550 nm. [c] The quantum yield for ZnTPP in toluene, used as a reference, is 0.033 (see ref. [12b]).
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Porphyrin-Appended Polynorbornenes
FULL PAPER
As shown in Figure 3, the Soret bands of 2d–f showed es-
sentially no change compared with those of the correspond-
ing monomers 1d–f. Presumably, little aggregation resulting
in exciton coupling may take place for 2d–f because of the
presence of four aryl substituents on the porphyrin ring.[15]
The fluorescence quantum yields of polymers 2a–c were
significantly reduced compared with those of the corre-
sponding monomers 1a–c, presumably due to self quench-
ing. It is interesting to note that the reduction in quantum
yield for polymers 2d–f compared with those of the corre-
sponding monomers 1d–f were, relatively speaking, smaller
than for those of alkyl-substituted analogues 2a–c. These re-
sults appear to be consistent with other photophysical data
and the NMR results described above.
N-aryl-pyrrolidenonorbornenes may have coherently aligned
pendant groups that exhibit exciton coupling and fluores-
cence quenching in the absorption and emission profiles. p–
p interactions between the pendant groups were essential to
dictate the photophysical properties of the polymers and the
mechanism for the stereoselective formation of 2. Our re-
sults suggest that the presence of the N-aryl group is essen-
tial for dictating the stereoselectivity of the ROMP of 1. Be-
cause of the close proximity between the porphyrin moiet-
ies, these polymers may provide a versatile model system
for studying light harvesting and photoinduced electron
transfer processes.
Experimental Section
Time-resolved fluorescence spectroscopy: Time-resolved
fluorescence decays for both monomers 1a–f and polymers
2a–f in CH2Cl2 were measured. Using two-exponential fit-
tings, the fluorescence lifetimes are also summarized in
Table 1.
The longer lifetimes for 2a–f were comparable with those
of corresponding monomers 1a–f. The major route for the
fluorescence decay (60–73%) occurred via the shorter life-
time path, presumably because of self-quenching between
neighboring porphyrin moieties in 2a–f. As can be seen
from Table 1, these lifetimes fall within the same range as
those obtained from related cofacial porphyrin dyads.[21]
Similar quenching behavior can also be found in chloro-
phyll- and dye-based systems.[22] These results again suggest
that all porphyrin pendants are coherently aligned in a simi-
lar direction.
General: High-resolution mass spectrometric measurements were ob-
tained by using
a Jeol-JMS-700 mass spectrometer using the FAB
method with a 3-nitrobenzyl alcohol matrix. Gel permeation chromatog-
raphy (GPC) was performed by using a Waters GPC machine with an
isocratic HPLC pump (1515) and a refractive index detector (2414). THF
was used as the eluent (flow rate=1.0 mLminÀ1). Waters Styragel HR2,
HR3, and HR4 columns (7.8ꢂ300 mm) were employed for determining
the relative molecular weight with polystyrene as the standard (Mn
values ranged from 375 to 3.5ꢂ106). Absorption spectra were measured
by using a Hitachi U-3310 spectrophotometer and emission spectra were
recorded by using a Hitachi F-4500 fluorescence spectrophotometer.
Quantum yields were obtained with ZnTPP in toluene as the reference
(F=0.033).
21H,23H-5-(4-Hydroxyphenyl)-10,15,20-tris
N
(5a):
TFA (1.5 mL, 10À2 m) was added slowly to a mixture of 3a (1.22 g,
10 mmol), 4a (6.01 g, 30 mmol), and pyrrole (2.79 mL, 40 mmol) in
CH2Cl2 (2 L), then the mixture was stirred for 2 h before being quenched
by the addition of DDQ (6.81 g, 30 mmol). After stirring for 1 h at RT,
NEt3 (5 mL) was added to neutralize TFA. The solvent was removed in
vacuo and the residue was purified by column chromatography on silica
gel (eluent CH2Cl2) to give 5a as a purple solid (650 mg, 8%). M.p. 87–
888C; 1H NMR (400 MHz, CDCl3): d=À2.65 (s, 2H; NH), 0.87–0.92 (m,
9H; CH3), 1.17–1.45 (m, 36H; CH2), 1.48–1.56 (m, 6H; CH2), 1.75–1.88
(m, 6H; CH2), 2.47–2.58 (m, 6H; CH2), 4.90–5.00 (m, 6H; CH2), 7.11 (d,
Importance of the endo-fused N-arylpyrrolidine moiety: In
spite of the large porphyrin pendant groups in 2, the stereo-
selectivity (trans double bonds) and syn orientation of the
pendants appeared to be similar to those of simple aryl-sub-
stituted 5,6-endo-pyrrolidine-fused polynorbornenes.[9] It
seems likely that p–p interactions would be essential for
controlling the stereochemistry of the polymerization during
the course of the ROMP process. To test the validity of this
hypothesis, ROMP of 12 was carried out under the usual
conditions to give 13 containing a mixture of cis and trans
double bonds (21:79) in 81% yield.
3J
(d, 3J
(H,H)=4.7 Hz, 2H), 9.52 ppm (d, 3J
ACHTUNGTRENNUNG
A
ACHTUNGTNER(NUNG H,H)=8.1 Hz, 2H; ArH), 8.83
N
ACHTUNGTRENNUNG
R
(100 MHz, CDCl3): d=14.1, 22.7, 29.3, 29.4, 29.64, 29.66, 29.71, 29.73,
30.6, 30.7, 31.9, 35.4, 35.8, 38.7, 38.9, 113.5, 117.7, 119.1, 119.3, 127.9,
128.2, 135.1, 135.5, 136.3, 155.2 ppm; IR (KBr): n˜ =3383, 3318, 3129,
2954, 2923, 2852, 1609, 1513, 1479, 1467, 1353, 1264, 1238, 964, 913,
791 cmÀ1; HRMS (FAB): m/z calcd for C59H85N4O: 865.6720 [M++H];
found: 865.6723.
21H,23H-5-{4-[2-(Methoxycarbonyl)-1-vinyl]phenyl)-10,15,20-tris-
AHCTUNGERTG(NNUN undecyl)porphyrin (5c): Boron trifluoride etherate (0.8 mL) was added
slowly to a solution of 3c (1.00 g, 5.26 mmol), 4a (3.16 g, 15.78 mol), and
pyrrole (1.5 mL, 21.03 mmol) in dry CH2Cl2 (2 L) under nitrogen and the
mixture was stirred at RT for 1 h. DDQ (7.16 g, 31.54 mmol) was added
and the mixture was stirred at RT for 1 h. The reaction mixture was neu-
tralized with NEt3 (5 mL) and the solvent was evaporated in vacuo. The
residue was purified by column chromatography on silica gel (eluent
hexane/CH2Cl2 1:1) to give 5c (0.41 g, 8%). M.p. 56–578C; 1H NMR
(400 MHz, CDCl3): d=À2.65 (s, 2H), 0.85–0.92 (m, 9H), 1.27–1.33 (brs,
36H), 1.50–1.56 (m, 6H), 1.76–1.81 (m, 6H), 2.49–2.53 (m, 6H), 3.94 (s,
3H), 4.90–4.99 (m, 6H), 6.76 (d, 3J
(H,H)=8.1 Hz, 2H), 8.06 (d, 3J(H,H)=16.1 Hz, 1H), 8.19 (d, 3J
8.1 Hz, 2H), 8.79 (d, 3J(H,H)=4.8 Hz, 2H), 9.39 (d, 3J
(H,H)=4.8 Hz,
2H), 9.50 (d, 3J(H,H)=4.8 Hz, 2H), 9.53 ppm (d, 3J
(H,H)=4.8 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=14.1, 22.7, 29.36, 29.38, 29.65, 29.69,
ACHTUNGTRENNUNG
Conclusions
G
U
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
We have demonstrated direct evidence to show that porphy-
rin-appended polynorbornenes derived from 5,6-endo-fused
E
ACHTUNGTRENNUNG
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T.-Y. Luh et al.
29.7, 30.5, 30.6, 31.9, 35.3, 35.7, 38.7, 38.9, 51.8, 53.4, 116.6, 118.3, 119.2,
119.6, 126.2, 127.9, 128.1, 130.6, 130.7, 133.5, 134.9, 144.8, 144.9,
167.5 ppm; IR (KBr): n˜ =3317, 3123, 3028, 2952, 2923, 2852, 1723, 1635,
1480, 1466, 1434, 1321, 1312, 1203, 1168, 983, 917, 790, 732 cmÀ1; HRMS
(FAB): m/z calcd for C63H89N4O2: 933.6986 [M++H]; found: 933.6978.
29.5, 31.9, 68.3, 112.7, 113.4, 119.7, 119.8, 120.5, 130.7, 131.0, 132.6, 134.5,
135.6, 135.7, 146.0, 159.0 ppm; IR (KBr): n˜ =3390, 3318, 2923, 2852, 1606,
1561, 1509, 1466, 1243, 1175, 966, 805, 741 cmÀ1; LRMS (MALDI): m/z
(%): 1016.5 (100) [M+ +3H]; HRMS (MALDI): m/z calcd for
C68H80N5O3: 1014.6232 [M++H]; found: 1014.6256; elemental analysis
calcd (%) for C68H79N5O3: C 80.51, H 7.85, N 6.90; found: C 80.29, H
8.26, N 6.35.
21H,23H-5-(4-Nitrophenyl)-10,15,20-tris(4-octyloxyphenyl)-porphyrin
(5d):[12] TFA (0.75 mL, 5ꢂ10À3 m) was added to a mixture of 3d (0.76 g,
5 mmol), 4b[23] (3.52 g, 15 mmol), and pyrrole (1.34 g, 20 mmol) in
CH2Cl2 (2 L) and stirred for 2.5 h, then quenched with DDQ (3.40 g,
15 mmol) for 1 h at RT. The solution was concentrated and filtered
through an alumina pad to remove the quinone and polypyrrylmethine
species. The solvent was removed in vacuo and the residue was purified
by column chromatography on silica gel (eluent hexane/CH2Cl2 7:3) to
give 5d (0.42 g, 8%). M.p. 202–2038C; 1H NMR (300 MHz, CDCl3): d=
5-{4-[2-(Methoxycarbonyl)-1-vinyl]phenyl}-10,15,20-tris-(undecyl)porphy-
AHCTUNGERTGrNNUN inzinc(II) (6a): Zinc acetate (730 mg, 3.32 mmol) was added to a solu-
tion of 5c (620 mg, 0.66 mmol) in methanol (10 mL) and CH2Cl2
(30 mL). The mixture was stirred at RT in the dark for 3 h and then
washed with NaHCO3 (5%) and brine and then dried (MgSO4). The sol-
vent was removed in vacuo to give a residue that was purified by column
chromatography on silica gel (eluent hexane/CH2Cl2/NEt3 1:1:0.05) to
afford 6a (580 mg, 88%). M.p. 89–908C; 1H NMR (400 MHz, CDCl3):
d=0.86–0.91 (m, 9H), 1.25–1.49 (m, 36H), 1.49–1.60 (m, 6H), 1.72–1.90
À2.74 (s, 2H; NH), 0.94 (t, 3J
ACHTUNGTRENNUNG
30H; CH2), 1.95 (quint, 3J(H,H)=6.3 Hz, 6H; CH2), 4.18 (t, 3J
ACTHNUGTRENNUGN ACHTUNGTRENNNUG
5.9 Hz, 6H; OCH2), 7.22 (d, 3J
(H,H)=8.4, 3.3 Hz, 6H; ArH), 8.31 (d, J
(d, J=8.4 Hz, 2H; ArH), 8.67 (d, J=4.8 Hz, 2H; b-H), 8.87 (s, 4H; b-H),
8.89 ppm (d, 3J(H,H)=4.8 Hz, 2H; b-H); 13C NMR (75 MHz, CDCl3):
ACHTUNGTRENNUNG
(m, 6H), 2.33–2.48 (m, 6H), 3.93 (s, 3H), 4.58 (t, 3J
4.72 (t, 3J(H,H)=7.8 Hz, 4H), 6.76 (d, 3J
(H,H)=16.1 Hz, 1H), 7.93 (d,
3J(H,H)=8.0 Hz, 2H), 8.06 (d, 3J(H,H)=16.1 Hz, 1H), 8.21 (d, 3J-
(H,H)=8.0 Hz, 2H), 8.84 (d, 3J(H,H)=4.7 Hz, 2H), 9.19 (d, 3J
(H,H)=
4.7 Hz, 2H), 9.22 (d, 3J(H,H)=4.7 Hz, 2H), 9.37 ppm (d, 3J
(H,H)=
ACHTUNGTREN(NUGN H,H)=7.8 Hz, 2H),
3
A
ACHTUNGTNER(NUNG H,H)=8.4 Hz, 2H; ArH), 8.55
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
d=14.1, 22.7, 26.3, 29.3, 29.5, 31.9, 68.4, 112.9, 114.8, 116.2, 120.5, 121.0,
121.8, 129.8, 131.4, 132.0, 134.1, 134.2, 135.1, 135.6, 146.9, 147.7, 149.4,
159.2 ppm; IR (KBr): n˜ =2925, 2855, 1606, 1510, 1469, 1347, 1284, 1245,
1174, 1108, 966, 847, 801, 735 cmÀ1; LRMS (MALDI): m/z (%): 1044.0
(100) [M+], 1045.0 (80) [M++H]; elemental analysis calcd (%) for
C68H77N5O5: C 78.20, H 7.43, N 6.71; found: C 78.34, H 7.84, N 5.90.
A
ACHTUNGTRENNUNG
4.7 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=14.3, 22.8, 29.5 29.80,
29.85, 29.88, 30.9, 32.0, 35.3, 35.5, 38.9, 39.0, 51.9, 117.3, 117.9, 119.7,
126.1, 128.0, 128.2, 128.4, 131.1, 133.1, 134.9, 144.8, 145.4, 148.1, 148.5,
148.8, 149.1, 167.4 ppm; IR (KBr): n˜ =3123, 3060, 3025, 2952, 2923, 2852,
1723, 1633, 1603, 1466, 1435, 1322, 1205, 1167, 1078, 1007, 986, 932, 787,
712 cmÀ1; HRMS (FAB): m/z calcd for C63H86N4O2Zn: 994.6042 [M+];
found: 994.6044.
21H,23H-5-(4-Hydroxyphenyl)-10,15,20-tris(4-octyloxyphenyl)-porphyrin
(5e);[24] TFA (1.5 mL, 10À2 m) was added slowly to a mixture of 4b
(7.02 g, 30 mmol), 3a (1.22 g, 10 mmol), and pyrrole (2.68 g, 40 mmol) in
CH2Cl2 (2 L) and the mixture was stirred for 2.5 h, then quenched by ad-
dition of p-chloranil (7.44 g, 30 mmol). After 3 h at RT, NaHCO3 (10 g)
was added to neutralize TFA. The crude mixture was concentrated and
filtered through an alumina pad to remove quinone and polypyrryl-
5-[4-(3-Hydroxy-1-propyl)phenyl]-10,15,20-tris-(undecyl)-porphyrin-
AHCTUNGTREGzNNUN inc(II) (6b): A mixture of 6a (500 mg, 0.50 mmol) and Pd/C (10 wt%,
50 mg, 0.05 mmol) in EtOH (10 mL) and THF (20 mL) was purged three
times with hydrogen. The reaction system was then charged with hydro-
gen to 1 atm and stirred at RT for 24 h. After filtration through Celite,
the filtrate was evaporated in vacuo to give the corresponding hydrogen-
ACHTUNGTRENNUNGmethene species. The solvent was removed in vacuo and the residue was
purified by column chromatography on silica gel (eluent CH2Cl2) to give
1
ated product (410 mg, 83%). M.p. 46–478C; H NMR (400 MHz, CDCl3):
5e as
a
purple solid (1.217 g, 12%). M.p. 228–2298C; 1H NMR
d=0.86–0.91 (m, 9H), 1.24–1.45 (m, 36H), 1.75–1.86 (m, 6H), 1.75–1.86
3
(300 MHz, CDCl3): d=À2.74 (s, 2H; NH), 0.93 (t, J
ACHTUNGTRENNUNG
ACTHNUTRGNEUNG
(m, 6H), 2.35–2.49 (m, 6H), 2.98 (t, 3J(H,H)=7.8 Hz, 2H), 3.34 (t, 3J-
CH3), 1.35–1.52 (m, 24H; CH2), 1.60 (quint., 3J
A
A
ACHTUNGTRENNUNG
3
CH2), 1.95 (quint., J
A
G
A
R
ACHTUNGTRENNUNG
4H; OCH2), 4.20 (t, 3J
A
A
ACHTUNGTRENNUNG
3
3
3
7.02 (d, J
U
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
R
ACHTUNGTRENNUNG
13C NMR (100 MHz, CDCl3): d=14.1, 22.7, 29.4, 29.7, 29.8, 30.68, 30.74,
31.0, 31.9, 35.2, 35.4, 36.0, 38.7, 38.8, 51.8, 118.5, 119.6, 126.3, 128.0, 128.2,
128.3, 131.6, 134.6, 139.4, 141.3, 148.2, 148.9, 149.3, 149.4, 173.6 ppm; IR
(KBr) n˜ =3123, 3018, 2958, 2923, 2852, 1743, 1526, 1502, 1466, 1437,
1344, 1210, 1077, 1008, 788, 712 cmÀ1; HRMS (FAB): m/z: calcd for
C63H88N4O2Zn: 996.6199 [M+]; found: 996.6192.
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
13C NMR (75 MHz, CDCl3): d=14.4, 22.9, 26.4, 29.5, 29.7, 32.1, 68.3,
112.5, 113.42, 113.43, 119.3, 119.68, 119.72, 130.8, 134.15, 134.18, 134.5,
135.33, 135.38, 135.41, 155.0, 158.61, 158.62 ppm; IR (KBr) n˜ =3357,
2924, 2852, 1605, 1571, 1509, 1467, 1349, 1283, 1244, 1174, 1108, 966, 840,
803, 738 cmÀ1; LRMS (MALDI): m/z (%): 1015.6 (100) [M++H], 1016.6
(72) [M++2]; HRMS (MALDI): m/z calcd for C68H79N4O4: 1015.6053
[M++H]; found: 1015.6096.
DIBAL-H (4.0 mL, 1.0m in THF, 4.0 mmol) was added slowly to a solu-
tion of hydrogenated product (800 mg, 0.8 mmol) in THF (20 mL) at 08C
and stirred under a N2 atmosphere. The reaction mixture was allowed to
stir for 2 h at RT, then quenched by slowly pouring into saturated NH4Cl.
After the remaining DIBAL-H was completely quenched, the gel-like or-
ganic layer was acidified with 6m HCl and extracted with CH2Cl2. The
combined organic layers were washed with NaOH (10%) and brine and
then dried (MgSO4) and evaporated in vacuo to afford 6b (730 mg,
94%). M.p. 50–518C; 1H NMR (400 MHz, CDCl3): d=0.86–0.91 (m,
21H,23H-5-(4-Aminophenyl)-10,15,20-tris(4-octoxyphenyl)-porphyrin
(5 f):[25]
A mixture of 5d (522 mg, 0.5 mmol), SnCl2·2H2O (564 mg,
2.5 mmol), and HCl (35%, 3 mL) in THF (25 mL) was stirred at RT
under argon for 24 h. The solvent was removed in vacuo and the residue
was dissolved in CH2Cl2 (50 mL). Sodium hydroxide (10%) was added
until the pH value was basic, then the organic layer was separated and
dried (MgSO4) and the solvent was removed in vacuo to give a residue
that was purified by column chromatography on silica gel (eluent
CH2Cl2) to give 5 f as a purple solid (0.38 g, 75%). M.p. 203–2068C;
9H), 1.13 (t, 3J
6H), 1.76–1.86 (m, 6H), 1.98–2.13 (m, 2H), 2.38–2.51 (m, 6H), 2.95 (t, J-
(H,H)=7.7 Hz, 2H), 3.61–3.67 (m, 2H), 4.65 (t, 3J
(H,H)=8.1 Hz, 2H),
(H,H)=7.9 Hz, 2H), 8.09 (d, 3J-
(H,H)=4.7 Hz, 2H), 9.25 (d, 3J
(H,H)=
(H,H)=4.7 Hz, 2H), 9.39 ppm (d, 3J
(H,H)=
ACHTUNGTREN(NGNU H,H)=5.3 Hz, 1H), 1.27–1.48 (m, 36H), 1.49–1.60 (m,
3
A
ACHTUNGTRENNUNG
3
3
1H NMR (300 MHz, CDCl3): d=À2.73 (s, 2H; NH), 0.93 (t, 3J
AHCTUNGTRENNUNG
4.77 (t, J
(H,H)=7.9 Hz, 2H), 8.88 (d, 3J
4.7 Hz, 2H), 9.27 (d, 3J
ACHTUGTNREN(UNG H,H)=8.1 Hz, 4H), 7.51 (d, JCAHTUNGTRENNNUG
6.6 Hz, 9H; CH3), 1.35–1.49 (m, 24H; CH2), 1.60 (quint., 3J
ACHTUNGTENR(NUNG H,H)=
E
A
ACHTUNGTRENNUNG
6.6 Hz, 6H; CH2), 1.95 (quint., 3J
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
4.7 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=14.1, 22.7, 29.4, 29.7, 29.8,
30.8, 31.8, 31.9, 33.9, 35.37, 35.44, 38.8, 38.9, 62.1, 118.7, 119.55, 119.62,
126.4, 128.1, 128.28, 128.33, 131.7, 134.5, 140.5, 140.8, 148.4, 149.0, 149.3,
149.4 ppm; IR (KBr): n˜ =3326, 3123, 3018, 2955, 2923, 2852, 1608, 1557,
2H; NH2), 4.19 (t, 3J
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
1525, 1502, 1466, 1343, 1298, 1209, 1076, 1056, 1009, 788, 712 cmÀ1
;
5724
www.chemeurj.org
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 5719 – 5728

Porphyrin-Appended Polynorbornenes
FULL PAPER
HRMS (FAB): m/z calcd for C62H88N4OZn: 968.6250 [M+]; found:
968.6257.
1058, 967, 791, 734 cmÀ1; HRMS (FAB): m/z calcd for C75H100N5O2:
1102.7877 [M++H]; found: 1102.7886.
Compound 11b: In a manner similar to that described above for 11a,
compound 5g[15] was converted to 11b (0.37 g, 74%). M.p. 90–918C;
1H NMR (400 MHz, CDCl3): d=À2.65 (s, 2H; NH), 0.86–0.92 (m, 9H;
CH3), 1.27–1.42 (m, 36H; CH2), 1.45–1.56 (m, 7H; CH2; CH on norbor-
4-{4-[(tert-Butoxycarbonyl)methoxycarbonyl]phenyl}-4-azatri-cy-
clo[5.2.1.02,6]dec-8-ene (9a): tert-Butyl bromoacetate (0.97 g, 5.0 mmol)
was added to a mixture of 7 (1.02 g, 4.0 mmol) and Cs2CO3 (0.65 g,
2.0 mmol) in DMF (25 mL), then the mixture was heated to 508C for
30 min before being cooled to RT. CH2Cl2 (70 mL) was added and the
mixture was poured into saturated NaHCO3. The organic layer was sepa-
rated and washed with aqueous NaHCO3 (3ꢂ50 mL) and water (2ꢂ
50 mL) and then dried (MgSO4), and the solvent was removed in vacuo
to give a residue that was flash purified by using column chromatography
(eluent hexane/EtOAc 2:1) to give 9a (1.40 g, 95%). M.p. 160–1628C;
nene), 1.63 (d, 2J
ACHTNUTRGNEUNG(H,H)=8.3 Hz, 1H; CH on norbornene), 1.77–1.85 (m,
6H; CH2), 2.50–2.56 (m, 6H; CH2), 2.97–3.01 (m, 4H; H on norbornene),
3.07–3.10 (m, 2H; H on norbornene), 3.29–3.32 (m, 2H; H on norbor-
nene), 4.91–4.98 (m, 6H; CH2), 5.70 (s, 2H; OCH2), 6.19 (s, 2H; alkenyl
H on norbornene), 6.47 (d, 3J
ACHTUNGTRENNUNG
A
E
3
3J
ACHTUNGTRENNUNG
1H NMR (300 MHz, CDCl3): d=1.48 (s, 9H; CH3), 1.52 (d, 2J
8.1 Hz, 1H; anti-10-H), 1.62 (d, 2J
(H,H)=8.1 Hz, 1H; syn-10-H), 2.94–
2.95 (m, 2H), 2.8 (s, 2H), 3.08–3.10 (m, 2H), 3.27–3.33 (m, 2H), 4.67 (s,
2H, CH2O), 6.17 (s, 2H; vinyl-H), 6.39 (d, 3J
(H,H)=9.0 Hz, 2H),
7.91 ppm (d, 3J(H,H)=9.0 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=
ACHTUNGTRNE(NUNG H,H)=
3J
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
9.53 ppm (d, 3J
d=14.3, 22.8, 29.46, 29.48, 29.75, 29.77, 29.8, 29.9, 30.7, 30.8, 32.0, 35.5,
35.9, 38.8, 39.0, 45.4, 46.6, 50.4, 52.1, 65.8, 110.7, 110.9, 116.1, 117.4, 119.0,
119.3, 125.9, 127.8 (br), 131.0, 131.4, 134.4, 135.6, 136.1, 142.0, 150.3,
166.9 ppm; IR (KBr): n˜ =3316, 3120, 3053, 2952, 2923, 2852, 1704, 1605,
1524, 1475, 1376, 1271, 1177, 1097, 969, 917, 792, 768 cmÀ1; HRMS
(FAB): m/z: calcd for 1116.8034 (C76H102N5O2, [M++H]); found:
1116.8024.
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
28.0, 45.4, 46.6, 50.4, 52.1, 61.1, 82.0, 110.9, 115.3, 131.6, 135.8, 150.6,
166.3, 167.6 ppm; IR (KBr): n˜ =2978, 2942, 2867, 1745, 1696, 1609, 1526,
1482, 1426, 1386, 1368, 1298, 1230, 1166, 1106, 771 cmÀ1; LRMS (ESI):
m/z (%): 370.2 (60) [M++H]; HRMS (ESI): m/z calcd for C22H27NO4:
370.2026 [M++H]; found: 370.2013.
21H,23H-5-[(4-Aza-tricycle[5.2.1.02,6-endo]dec-8-ene-3,5-dione-4-yl)phen-
4-{4-[(Hydroxycarbonyl)methoxycarbonyl]phenyl}-4-azatri-cyclo
[5.2.1.02,6]dec-8-ene (9b):
A solution of 9a (1.11 g, 3.0 mmol) and
yl]-10,15,20-tris(4-octoxyphenyl)porphyrin (11d):
A solution of 10
(43 mg, 0.26 mmol) and 5 f (267 mg, 0.26 mmol) in DMF (5 mL) was
heated at reflux for 18 h. The solvent was removed in vacuo and the resi-
due was purified by column chromatography on silica gel (eluent
CH2Cl2) to give the corresponding imide 11d’ as a purple solid (201 mg,
67%). M.p. >3008C; 1H NMR (300 MHz, CDCl3): d=À2.76 (s, 2H;
CF3CO2H (50%) in CH2Cl2 (30 mL) was stirred for 3 h and then evapo-
rated in vacuo to afford an oily residue. A small amount of water was
added and the mixture was neutralized with saturated NaHCO3. The
white precipitate was collected and washed with water and hexane and
then dried under vacuum to give 9b (1.0 g, 91%). M.p. 200–2018C;
1H NMR (300 MHz, CDCl3): d=1.49 (apparent s, 2H; bridging CH2),
2.90–2.94 (m, 4H), 3.06–3.8 (m, 2H), 3.25–3.29 (m, 2H), 4.70 (s, 2H;
NH), 0.94 (t, 3J
(quint., 3J
10-H), 1.86 (d, 2J
6.6 Hz, 6H; CH2), 3.55 (brs, 2H; H on norbornene), 3.62 (brs, 2H; H on
ACHTUNGTRENNUNG
ACHUTNGRENNUG CAHTUNGTRENNUNG
(H,H)=6.6 Hz, 6H; CH2), 1.67 (d, 2J
A
ACHTUNGTRENNUNG
CH2O), 6.17 (s, 2H; vinyl-H), 6.45 (d, 3J
(H,H)=9.0 Hz, 2H), 7.75 (d, 3J-
ACHTUNGTRENNUNG
(H,H)=9.0 Hz, 2H), 12.99 ppm (brs, 1H; COOH); 13C NMR (100 MHz,
3
norbornene), 4.22 (t, J
H), 7.25 (d, 3J(H,H)=8.1 Hz, 6H; ArH), 7.55 (d, 3J
ArH), 8.09 (d, 3J(H,H)=8.1 Hz, 6H; ArH), 8.26 (d, 3J
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
CDCl3): d=44.7, 46.0, 50.0, 51.5, 60.3, 111.0, 114.4, 130.9, 135.7, 150.3,
165.4, 169.5 ppm; IR (KBr): n˜ =3060, 2964, 2941, 2886, 2848, 1735, 1714,
A
ACHTUNGTRENNUNG
E
1608, 1526, 1477, 1433, 1411, 1379, 1278, 1244, 1188, 1122, 767 cmÀ1
;
2H; ArH), 8.87 ppm (brs, 8H; b-H); 13C NMR (75 MHz, CDCl3): d=
14.2, 22.7, 26.2, 29.3, 29.5, 29.7, 31.9, 45.6, 45.9, 52.3, 68.2, 112.7, 118.3,
120.0, 120.3, 124.7, 130.7, 131.0, 131.4, 134.2, 134.8, 135.0, 135.6, 142.4,
158.9, 177.0 ppm; IR (KBr): n˜ =2925, 2854, 1713, 1606, 1509, 1468, 1376,
1283, 1245, 1174, 1108, 966, 738, 723 cmÀ1; LRMS (MALDI): m/z (%):
1161.6 (100) [M++2H]; HRMS (MALDI): m/z calcd for C77H86N5O5:
1160.6615 [M++H]; found: 1160.6624.
LRMS (ESI): m/z (%): 312.2 ([M+ÀH] (100); HRMS (ESI): m/z calcd
for C18H20NO4: 314.1397 [M++H]; found: 314.1387; elemental analysis
calcd (%) for C18H19NO4: C 68.99, H 6.11, N 4.47; found: C 68.44, H
6.12, N 4.28.
Compound 11a: Oxalyl chloride (0.31 mL, 3.7 mmol) and DMF (one
drop) were added to a solution of 7 (390 mg, 1.5 mmol) in CH2Cl2
(20 mL) at 08C. The mixture was gradually warmed to RT and stirred for
1 h, then the solvent was removed in vacuo to give 8, which was used for
the next reaction without further purification.
A solution of imide 11d’ (200 mg, 0.17 mmol) in CH2Cl2 (10 mL) was
added slowly to a suspension of LiAlH4 (26 mg, 0.68 mmol) in Et2O
(10 mL), and the mixture was stirred at RT for 4 h. Water (1 mL) and
NaOH (10%, 1 mL) were then added sequentially and the resulting sus-
pension was filtered. The solid was repeatedly triturated with CH2Cl2 and
then filtered. The CH2Cl2 solution was dried (Na2SO4) and filtered and
the filtrate was concentrated in vacuo to give a residue that was purified
by column chromatography on silica gel (eluent hexane/CH2Cl2 1:1) to
Next, compound 8 in CH2Cl2 (20 mL) was added to a mixture of 5a
(880 mg, 1.0 mmol), NEt3 (2.0 mL), and DMAP (trace amount) in
CH2Cl2 (20 mL) at 08C. The mixture was stirred at RT for 17 h, then sa-
turated NaHCO3 was added and the solution was washed with water and
brine and then dried (MgSO4). The solvent was removed in vacuo and
the residue was purified by column chromatography on silica gel (eluent
hexane/CH2Cl2/NEt3 1:1:0.05) to give 11a (1.03 g, 93%). M.p. 92–938C;
1H NMR (400 MHz, CDCl3): d=À2.64 (s, 2H; NH), 0.87–0.93 (m, 9H;
CH3), 1.25–1.47 (m, 36H; CH2), 1.47–1.62 (m, 7H; CH2; CH on norbor-
give 11d as a purple solid (135 mg, 70%). M.p. 204–2068C; 1H NMR
3
(300 MHz, CDCl3): d=À2.69 (s, 2H; NH), 0.94 (t, J
ACHTUNGTREN(NGNU H,H)=6.6 Hz, 9H;
CH3), 1.35–1.71 (m, 32H; CH2 on alkyl chain and norbornene), 1.97
(quint., 3J
(H,H)=6.6 Hz, 6H; CH2), 3.09–3.21 (m, 6H; H on norbor-
nene), 3.45–3.51 (m, 2H; H on norbornene), 4.22 (t, 3J
(H,H)=6.6 Hz,
6H; OCH2), 6.34 (t, 3J
(H,H)=1.5 Hz, 2H; alkenyl H on norbornene),
6.78 (d, 3J(H,H)=8.4 Hz, 2H; ArH), 7.25 (d, 3J
(H,H)=8.4 Hz, 6H;
ArH), 8.01 (d, 3J(H,H)=8.4 Hz, 2H; ArH), 8.10 (d, 3J
(H,H)=8.4 Hz,
2H; ArH), 8.83 (d, 3J
(H,H)=4.8 Hz, 2H; b-H), 8.84 (s, 4H; b-H),
8.93 ppm (d, 3J(H,H)=4.8 Hz, 2H; b-H); 13C NMR (75 MHz, CDCl3):
AHCTUNGTRENNUNG
nene), 1.65 (d, 2J
ACHTUNGTRENNUNG(H,H)=8.2 Hz, 1H; CH on norbornene), 1.78–1.87 (m,
6H; CH2), 2.50–2.58 (m, 6H; CH2), 3.00–3.04 (m, 4H; H on norbornene),
3.06–3.09 (m, 2H; H on norbornene), 3.29–3.34 (m, 2H; H on norbor-
nene), 4.91–4.98 (m, 6H; CH2), 6.21 (s, 2H; alkenyl H on norbornene),
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
6.53 (d, 3J
ArH), 8.20 (d, 3J
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
3
3
2H; ArH), 8.90 (d, J
N
ACHTUNGTRENNUNG
d=14.1, 22.7, 26.3, 29.4, 29.5, 29.7, 31.9, 45.8, 46., 51.0, 52.3, 68.4, 110.4,
112.7, 119.3, 119.6, 121.5, 129.4, 130.8, 130.8, 130.9, 131.0, 131.2, 131.2,
131.3, 134.6, 134.7, 135.6, 135.9, 136.1, 147.2, 158.9 ppm; IR (KBr): n˜ =
2H; b-H), 9.51 (d, 3J
U
ACHTUNGTRENNUNG
4.8 Hz, 2H; b-H); 13C NMR (100 MHz, CDCl3): d=14.3, 22.8, 29.5,
29.77, 29.84, 29.86, 30.7, 30.8, 32.0, 35.5, 35.9, 38.8, 39.0, 45.4, 46.7, 50.5,
52.1, 111.0, 115.2, 117.1, 119.0, 119.3, 120.0 127.9, 128.3, 132.0, 135.0,
135.6, 139.4, 150.6, 151.0, 165.6 ppm; IR (KBr): n˜ =3313, 3126, 3060,
2955, 2923, 2852, 1721, 1603, 1527, 1474, 1380, 1272, 1205, 1175, 1164,
2924, 2853, 1607, 1509, 1469, 1367, 1284, 1244, 1174, 965, 803, 738 cmÀ1
;
LRMS (MALDI): m/z (%): 1067.1 (100) [M+ÀC4H3N2À], 1132.1 (6)
[M+], 1133.1 (10) [M++H], 1134.1 (10) [M+ +2H]; HRMS (MALDI):
m/z calcd for C77H90N5O3: 1132.7015 [M++H]); found: 1132.7038.
Chem. Eur. J. 2009, 15, 5719 – 5728
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5725

T.-Y. Luh et al.
Compound 11e: Compound 8 in CH2Cl2 (10 mL) was added dropwise to
a mixture of 5e (507 mg, 0.5 mmol) and DMAP (0.75 mol, 92 mg) in
CH2Cl2 (10 mL) at 08C under argon. The mixture was allowed to warm
to RT and was stirred for an additional 24 h. After removal of the solvent
in vacuo, the residue was purified by column chromatography on silica
gel (eluent CH2Cl2/hexane 3:1) to give 11e as a purple solid (594 mg,
95%). M.p. 229–2318C; 1H NMR (300 MHz, CDCl3): d=À2.76 (s, 2H;
1059, 1008, 788 cmÀ1
;
HRMS (FAB): m/z calcd for C75H97N5O2Zn:
1163.6934 [M+]; found: 1163.6943.
Compound 1b: In a manner similar to that described above for 1a, com-
pound 11b (320 mg, 0.287 mmol) was converted to 1b (301 mg, 89%).
M.p. 68–698C; 1H NMR (400 MHz, CDCl3): d=0.89–0.96 (m, 9H; CH3),
1.30–1.45 (m, 36H; CH2), 1.45–1.60 (m, 7H; CH2; CH on norbornene),
1.64 (d, 2J
ACTHNUTRGNE(NUG H,H)=8.4 Hz, 1H; CH on norbornene), 1.70–1.85 (m, 6H;
NH), 0.94 (t, 3J
(quint., 3J
2H), 3.35–3.41 (m, 2H), 4.25 (t, J
2H), 6.52 (d, 3J(H,H)=9.0 Hz, 2H), 7.27 (d, 3J
(d, 3J(H,H)=9.0 Hz, 2H), 8.11 (d, 3J(H,H)=9.0 Hz, 6H), 8.18 (d, 3J-
(H,H)=9.0 Hz, 2H), 8.23 (d, 3J
(H,H)=9.0 Hz, 2H), 8.87 (s, 4H, b-H),
8.89 (d, 3J(H,H)=5.1 Hz, 2H, b-H), 8.90 ppm (d, 3J
(H,H)=5.1 Hz, 2H,
ACHTUNGTRENNUNG
CH2), 2.26–2.28 (m, 2H; CH2), 2.41–2.43 (m, 4H; CH2), 2.95–2.99 (m,
4H; H on norbornene), 3.06–3.08 (m, 2H; H on norbornene), 3.24–3.29
(m, 2H; H on norbornene), 4.35–4.39 (m, 2H; CH2), 4.60–6.64 (m, 4H;
CH2), 5.69 (s, 2H; OCH2), 6.19 (s, 2H; alkenyl H on norbornene), 6.43
ACHTUNGTRENNUNG
3
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(d, 3J
8.06 (d, 3J
ArH), 8.88 (d, JACTHNUGRTEN(NUNG H,H)=4.8 Hz, 2H; b-H), 8.98 (d, JACHTUNGTERN(NUGN H,H)=4.0 Hz, 2H;
(H,H)=8.8 Hz, 2H; ArH), 7.84 (d, 3J
(H,H)=8.0 Hz, 2H; ArH),
(H,H)=8.0 Hz, 2H;
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
R
ACHTUNGTRENNUNG
3
3
A
ACHTUNGTRENNUNG
b-H); 13C NMR (75 MHz, CDCl3): d=14.2, 22.7, 26.2, 29.3, 29.5, 31.9,
45.4, 46.6, 50.5, 52.1, 68.3, 111.1, 112.7, 115.2, 118.9, 119.9, 120.1, 120.2,
131.0 (br), 132.1, 134.3, 134.4, 135.3, 135.6, 135.8, 139.3, 150.8, 151.3,
158.9, 165.8 ppm; IR (KBr): n˜ =2924, 2851, 1722, 1604, 1558, 1506, 1471,
1379, 1277, 1244, 1175, 1057, 966, 802, 720 cmÀ1; LRMS (MALDI): m/z
(%): 1252.7 (100) [M++H]; HRMS (MALDI): m/z calcd for C84H94N5O5:
1252.7222 [M++H]; found: 1252.7250; elemental analysis calcd (%) for
C84H94N5O5: C 80.54, H 7.48, N 5.59; found: C 80.07, H 7.51, N 5.11.
3
3
b-H), 9.03 (d, JACTHNUTRGNENGU(H,H)=4.8 Hz, 2H; b-H), 9.33 ppm (d, JACHTUGNTREN(NUGN H,H)=5.2 Hz,
2H; b-H); 13C NMR (100 MHz, CDCl3): d=14.6, 23.1, 29.7, 30.0, 30.1,
31.1, 32.3, 35.7, 39.1, 39.2, 45.6, 46.8, 50.6, 52.3, 65.9, 110.7, 115.9, 118.0,
119.36, 119.43, 125.5, 127.3, 127.9, 128.1, 131.1, 131.3, 134.0, 135.35,
135.41, 142.3, 147.8, 148.4, 148.6, 148.9, 149.9, 166.5 ppm; IR (KBr): n˜ =
3063, 2952, 2923, 2852, 1704, 1604, 1523, 1466, 1375, 1271, 1177, 1096,
1008, 788 cmÀ1; HRMS (ESI): m/z calcd for C76H99N5O2Zn: 1177.7090
[M+]; found: 1177.7075.
Compound 11 f: A mixture of 9b (250 mg, 0.8 mmol) and oxalyl chloride
(0.75 mL, 8 mmol) in CH2Cl2 (10 mL) was stirred at RT for 3 h and dried
in vacuo to give 9c, which was used for the next reaction without further
Compound 1c: In a manner similar to that described for the preparation
of 11a, a mixture of 6b (500 mg, 0.51 mmol), NEt3 (1.0 mL), DMAP
(trace amount), and 8 (200 mg, 0.77 mmol; freshly prepared from 7) in
CH2Cl2 (10 mL) was converted to 1c (410 mg, 67%). M.p. 65–668C;
1H NMR (400 MHz, CDCl3): d=0.88–0.93 (m, 9H; CH3), 1.28–1.46 (m,
36H; CH2), 1.46–1.66 (m, 8H), 1.77–1.90 (m, 6H; CH2), 2.31–2.54 (m,
purification.
A mixture of 5e (507 mg, 0.5 mmol) DMAP (96 mg,
0.8 mol) and 9c in CH2Cl2 (20 mL) was stirred at RT for 24 h. The sol-
vent was removed in vacuo and the residue was purified by column chro-
matography on silica gel (eluent hexane/CH2Cl2 3:7) to give 11 f (622 mg,
95%). M.p. 202–2048C; 1H NMR (300 MHz, CDCl3): d=À2.78 (s, 2H;
8H), 2.94–2.98 (m, 4H), 3.04–3.07 (m, 2H), 3.18 (t, 3J
2H), 3.24–3.29 (m, 2H), 4.53–4.56 (m, 4H), 4.74 (t, 3J
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
NH), 0.94 (t, 3J
(quint., 3J
nene), 3.08–3.11 (m, 2H; H on norbornene), 3.29–3.35 (m, 2H; H on nor-
bornene), 4.24 (t, 3J
(H,H)=6.6 Hz, 6H; 3ꢂOCH2), 5.20 (s, 2H;
OCH2CO), 6.18 (s, 2H; vinyl-H), 6.44 (d, 3J
(H,H)=8.7 Hz, 2H; ArH),
7.26 (d, 3J(H,H)=8.4 Hz, 6H; ArH), 7.54 (d, 3J
(H,H)=8.7 Hz, 2H;
ArH), 8.03 (d, 3J
(H,H)=8.7 Hz, 2H; ArH), 8.09 (d, J=8.4 Hz, 6H;
ACHTUNGTRENNUNG(H,H)=6.6 Hz, 9H; CH3), 1.36–1.67 (m, 32H; CH2), 1.98
4H), 6.16 (s, 2H), 6.42 (d, 3J(H,H)=8.8 Hz, 2H), 7.62 (d, 3J
ACTHNUGTRENNUGN ACHTUNGTRENNUNG
A
7.8 Hz, 2H), 7.98 (d, 3J
2H), 8.90 (d, 3J(H,H)=5.0 Hz, 2H), 9.16 (d, 3J
(d, 3J(H,H)=4.4 Hz, 2H), 9.38 ppm (d, 3J
(H,H)=8.8 Hz, 2H), 8.12 (d, 3J
ACHUTGTNRENNUG CAHTUNGTRENNUNG
N
ACHTUNGTRENNUNG
E
N
ACHTUNGTRENNUNG
G
(100 MHz, CDCl3): d=14.1, 22.7, 29.4, 29.69, 29.75, 29.77, 30.66, 30.74,
30.80, 31.9, 32.5, 35.0, 35.3, 38.6, 38.8, 45.3, 46.5, 50.4, 52.3, 63.6, 110.9,
116.6, 118.7, 119.3, 119.4, 126.6, 127.8, 128.0, 128.3, 131.2, 131.7, 134.6,
135.7, 140.4, 140.9, 148.0, 148.7, 149.3, 150.4, 167.2 ppm; IR (KBr): n˜ =
3120, 3063, 3022, 2952, 2923, 2852, 1704, 1605, 1524, 1467, 1377, 1274,
1179, 1104, 1077, 1008, 788, 769, 713 cmÀ1; HRMS (FAB): m/z calcd for
C78H103N5O2Zn: 1205.7403 [M++H]; found: 1205.7410.
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ArH), 8.21 (d, J=8.7 Hz, 2H; ArH), 8.81–8.88 ppm (m, 8H, b-H);
13C NMR (100 MHz, CDCl3): d=14.2, 22.7, 26.2, 29.3, 29.46, 29.47, 31.9,
45.3, 46.5, 50.3, 52.0, 60.9, 68.2, 111.0, 112.6, 112.7, 114.8, 118.4, 119.6,
119.8, 120.0, 120.2, 131.1, 131.8, 134.26, 134.29, 134.34, 135.3, 135.5, 135.6,
135.7, 140.1, 150.1, 150.7, 158.9, 166.5, 167.3 ppm; IR (KBr): n˜ =2926,
2853, 1745, 1712, 1605, 1507, 1470, 1378, 1283, 1245, 1169, 1104, 966, 801,
768, 720 cmÀ1; LRMS (MALDI): m/z (%): 1310.7 [M++H] (81); HRMS
(MALDI): m/z calcd for C86H96N5O7: 1310.7318 [M++H]; found:
1310.7304.
Compound 1d: In a manner similar to that described for 1a, compound
11d (113 mg, 0.1 mmol) was converted to 1d (113 mg, 95%). M.p. 200–
2028C; 1H NMR (300 MHz, CDCl3): d=0.94 (t, 3J
ACHTUNGTRENNUNG
CH3), 1.36–1.72 (m, 32H), 1.97 (quint., 3J
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
OCH2), 6.35 (s, 2H), 6.78 (d, 3J
G
ACHTUNGTRENNUNG
Compound 1a: A mixture of 11a (700 mg, 0.63 mmol) and zinc acetate
(690 mg, 3.15 mmol) in methanol (20 mL) and CH2Cl2 (40 mL) was
stirred at RT in the dark for 3 h and then washed with NaHCO3 and
brine and dried (MgSO4). The solvent was removed in vacuo to give a
residue that was purified by column chromatography on silica gel (eluent
hexane/CH2Cl2/NEt3 1:1:0.05) to afford 1a (680 mg, 92%). M.p. 136–
1378C; 1H NMR (400 MHz, CDCl3): d=0.85–0.90 (m, 9H; CH3), 1.27–
1.42 (m, 36H; CH2), 1.46–1.61 (m, 7H; CH2; CH on norbornene), 1.65
8.4 Hz, 6H), 8.01 (d, 3J
A
ACHTUNGTRENNUNG
3
6H), 8.94 (d, J
(H,H)=4.8 Hz, 2H; b-H), 8.95 (s, 4H; b-H), 9.05 ppm (d,
J=4.8 Hz, 2H; b-H); 13C NMR (75 MHz, CDCl3): d=14.2, 22.7, 26.3,
29.4, 29.6, 29.7, 31.9, 45.8, 46.7, 51.0, 52.4, 68.4, 110.3, 112.6, 120.4, 120.7,
122.4, 130.0, 131.6, 131.7, 131.8, 132.3, 135.2, 135.4, 135.6, 136.1, 147.1,
150.36, 150.44, 150.5, 151.0, 158.8 ppm; IR (KBr): d=2924, 2853, 1606,
1573, 1524, 1509, 1489, 1468, 1374, 1338, 1281, 1245, 1173, 996, 796,
724 cmÀ1
;
LRMS (MALDI): m/z (%): 1127.3 (100) [M+ÀZnÀ2H],
(d, 2J
ACHTUNGTRENNUNG(H,H)=8.0 Hz, 1H; CH on norbornene), 1.72–1.85 (m, 6H; CH2),
2.30–2.38 (m, 2H; CH2), 2.39–2.49 (m, 4H; CH2), 3.00–3.04 (m, 4H; H
on norbornene), 3.09–3.11 (m, 2H; H on norbornene), 3.30–3.35 (m, 2H;
1128.3 (90) [M+ÀZnÀH], 1129.3 (88) [M+ÀZn], 1179.4 (20) [M+
ÀZn+CH3OH+H2O], 1193.3 (18) [M
+A(Zn64)], 1195.3 (16) [M+A(66Zn)],
CHUTGTNRENNUG CHTUNGTRENNUNG
1197.3 (14) [M CTHNUGTRNENUG
+A(68Zn)]; HRMS (MALDI): m/z calcd for
3
3
H on norbornene), 4.52 (t, J
7.8 Hz 4H; CH2), 6.20 (s, 2H; alkenyl H on norbornene), 6.49 (d, 3J-
(H,H)=8.8 Hz, 2H; ArH), 7.60 (d, 3J
(H,H)=8.8 Hz, 2H; ArH), 8.19 (d,
3J(H,H)=8.8 Hz, 2H; ArH), 8.20 (d, 3J
(H,H)=8.8 Hz, 2H; ArH), 8.92
ACHTUTNGRENNUG(H,H)=8.4 Hz 2H; CH2), 4.71 (t, JACHTUGNTREN(NUGN H,H)=
C77H87N5O364Zn: 1193.6092; found: 1193.6095.
G
ACHTUNGTRENNUNG
Compound 1e: In a manner similar to that described for 1a, compound
11e (500 mg, 0.4 mmol) was converted to 1e (510 mg, 97%). M.p. 226–
E
ACHTUNGTRENNUNG
3
3
2288C; 1H NMR (300 MHz, CDCl3): d=0.93 (t, 3J
ACHTUNGTRENNUNG
(d, J
N
ACHTUNGTNER(NUNG H,H)=4.8 Hz, 2H; b-H), 9.16
(d, 3J
ACHTUNGTRENNUNG
CH3), 1.35–1.63 (m, 32H; CH2), 1.95 (quint., 3J
ACHTUNGTRENNUNG
13C NMR (100 MHz, CDCl3): d=14.3, 22.8, 29.5, 29.79, 29.83, 29.88, 30.9,
32.0, 35.6, 35.7, 38.97, 39.02, 45.5, 46.8, 50.6, 52.2, 111.1, 115.3, 118.0,
119.8, 119.9, 128.3, 128.5, 131.7, 132.0, 134.9, 135.7, 140.1, 148.4, 149.1,
149.2, 149.4, 150.7, 150.8, 165.6 ppm; IR (KBr): n˜ =3123, 3060, 2955,
2923, 2852, 1721, 1605, 1527, 1500, 1468, 1380, 1272, 1205, 1175, 1164,
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
U
ACHTUNGTRENNUNG
3
AHCTUNGERTG(NNUN H,H)=8.4 Hz, 6H), 8.12
N
ACHTUNGTRENNUNG
5726
www.chemeurj.org
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 5719 – 5728

Porphyrin-Appended Polynorbornenes
FULL PAPER
3
3
b-H), 8.99 (d, J
G
G
Polymer 2d: Yield 80%; 1H NMR (500 MHz, CDCl3): d=0.89 (brs, 9H;
CH3), 1.28–2.00 (brm, 38H), 2.20–3.06 (brm, 8H), 3.40–4.23 (brm, 6H,
OCH2), 4.80–5.60 (brm, 2H), 6.71–7.28 (brm, 8H), 7.71–8.12 (brm, 8H),
8.67–8.96 ppm (brm, 8H; b-H); 13C NMR (125 MHz, CDCl3): d=14.1,
22.7, 26.1, 29.3, 29.5, 29.7, 31.8, 44.5, 45.0, 46.2, 50.2 (br), 68.2 (br), 111.4,
112.2, 112.3, 112.5, 120.3, 121.8, 129.5, 131.5, 131.8, 132.1, 135.3, 135.4,
147.4, 150.2, 150.5, 150.7, 158.5 ppm; IR (KBr): n˜ =3033, 2922, 2852,
1606, 1572, 1524, 1509, 1467, 1365, 1338, 1245, 1172, 1106, 1066, 996 (s),
846 (w), 797 (s), 718 cmÀ1 (w); GPC (THF): Mn =10550, Mw =14550,
PDI=1.38.
Polymer 2e: Yield 92%; 1H NMR (400 MHz, CDCl3): d=0.85 (brs, 9H;
CH3), 1.23–1.98 (m, 38H; CH2), 2.20–3.30 (br, 8H), 3.80–4.25 (br, 6H,
OCH2), 5.14 (brs, 2H), 6.34 (brs, 2H), 6.87–7.26 (m, 6H), 7.57 (brs, 2H),
7.85–8.20 (m, 10H), 8.85 ppm (brs, 8H; b-H); 13C NMR (100 MHz,
CDCl3): d=14.2, 22.7, 26.1, 29.3, 29.4, 31.8, 39.8, 44.4, 46.8, 49.2, 68.1,
111.6, 112.5, 116.2, 119.8, 120.8, 131.9, 135.3, 140.1, 150.0, 150.4, 151.0,
158.5, 158.7, 165.5 ppm; IR (KBr): n˜ =2924, 2853, 1725, 1606, 1525, 1509,
1491, 1380, 1339, 1265, 1246, 1205, 1175, 1064, 998, 798, 760, 720 cmÀ1; el-
emental analysis calcd (%): C 76.66, H 6.97, N 5.32; found: C 75.37, H
7.14, N 4.90; GPC (THF): Mn =51437, Mw =81295, PDI=1.58.
Polymer 2 f: Yield 92%; 1H NMR (300 MHz, CDCl3): d=0.91 (brs, 9H;
CH3), 1.32–1.81 (m, 38H; CH2), 2.60–2.98 (m, 8H; H on norbornene),
3.95–4.13 (m, 6H; 3ꢂOCH2), 5.82 (brs, 2H; OCH2CO), 5.19 (brs, 2H;
vinyl-H), 6.25 (brs, 2H; ArH), 7.01–7.17 (m, 6H; ArH), 7.37 (brs, 2H;
ArH), 7.67 (brs, 2H; ArH), 7.93–8.05 (m, 8H; ArH), 8.85–8.91 ppm (m,
8H; b-H); 13C NMR (100 MHz, CDCl3): d=14.1, 22.7, 26.2, 29.3, 29.4,
31.8, 35.7, 37.4, 39.7, 44.3, 46.2, 49.3, 60.6, 68.2, 111.3, 112.5, 115.3, 119.3,
120.8, 121.0, 126.0, 128.4, 131.6, 131.9, 132.0, 134.96, 135.0, 135.1, 135.3,
135.4, 140.7, 149.9, 150.4, 150.5, 151.1, 158.5, 158.6, 166.0, 167.0 ppm; IR
(KBr): n˜ =2925, 2853, 1745, 1716, 1606, 1524, 1509, 1491, 1378, 1339,
1281, 1245, 1204, 1172, 1105, 998, 798, 798, 767, 719 cmÀ1; GPC (THF):
Mn =9500, Mw =11000, PDI=1.16.
2H; b-H); 13C NMR (100 MHz, CDCl3): d=14.1, 22.7, 26.2, 29.3, 29.5,
29.7, 31.9, 45.3, 46.6, 50.5, 52.1, 68.3, 110.8, 111.1, 112.6, 115.3, 119.98,
120.04, 120.9, 121.0, 131.1, 131.8, 131.9, 132.0, 132.1, 135.00, 135.04, 135.1,
135.4, 135.8, 139.9, 150.2, 150.48, 150.54, 150.6, 150.8, 151.1, 158.76,
158.78, 165.8 ppm; IR (KBr): n˜ =2924, 2852, 1722, 1603, 1525, 1509, 1491,
1472, 1379, 1338, 1273, 1245, 1204, 1174, 1060, 998, 797, 720 cmÀ1; LRMS
(MALDI): m/z (%): 1313.6 (60) [M+]; HRMS (MALDI): m/z calcd for
C84H91N5O5Zn: 1313.6281 [M+]); found: 1313.6306; elemental analysis
calcd (%) for C84H91N5O5Zn: C 76.66, H 6.97, N 5.32; found: C 75.86, H
7.32, N 4.93.
Compound 1 f: In a manner similar to that described for 1a, compound
11 f (131 mg, 0.1 mmol) was converted to 1 f (115 mg, 88%). M.p. 199–
2018C; 1H NMR (300 MHz, CDCl3): d=0.94 (t, 3J
ACHTUNGTRENNUNG
CH3), 1.36–1.60 (m, 32H; CH2), 1.96 (quint., 3J
ACHTUNGTRENNUNG
3
bornene), 3.21–3.27 (m, 2H; H on norbornene), 4.21 (t, J
6H; 3ꢂOCH2), 5.07 (s, 2H; OCH2CO), 6.16 (s, 2H; vinyl-H), 6.36 (d, J-
(H,H)=8.7 Hz, 2H; ArH), 7.24 (d, 3J
(H,H)=8.4 Hz, 6H; ArH), 7.50 (d,
3J(H,H)=8.7 Hz, 2H; ArH), 7.89 (d, 3J
(H,H)=8.7 Hz, 2H; ArH), 8.09
(d, 3J(H,H)=8.4 Hz, 6H; ArH), 8.20 (d, 3J
(H,H)=8.7 Hz, 2H; ArH),
A
N
U
8.91–8.98 ppm (m, 8H; b-H); 13C NMR (100 MHz, CDCl3): d=14.1, 22.7,
26.2, 29.3, 29.5, 31.9, 45.3, 46.6, 50.4, 52.1, 60.8, 68.3, 111.0, 112.6, 114.7,
118.4, 119.4, 119.8, 121.0, 131.6, 131.7, 131.86, 131.92, 132.0, 132.1, 134.96,
135.0, 135.1, 135.4, 135.8, 140.8, 149.9, 150.0, 150.49, 150.52, 150.6, 150.7,
158.8, 166.4, 167.3 ppm; IR (KBr): n˜ =2926, 2854, 1784, 1712, 1605, 1573,
1525, 1509, 1492, 1473, 1379, 1339, 1282, 1245, 1172, 1105, 998, 797,
720 cmÀ1
;
LRMS (MALDI): m/z (%): 1371.6 (80) [M+]; HRMS
(MALDI): m/z calcd for C86H93N5O7Zn: 1371.6392 [M+]; found:
1371.6361.
General procedure for the preparation of polymer 2: A solution of 1
(0.2 mmol) and [RuACHTUNGTRENNUNG(=CHPh)Cl2CAHTUNGTRNE(NUGN Cy3P)2] (8 mg, 0.001 mmol, 5 mol%) in
CH2Cl2 (2 mL) was stirred at RT for 2 h Under argon. The mixture was
quenched with ethyl vinyl ether (1 mL) and poured into MeOH (10 mL).
The resulting solid was collected and redissolved in CH2Cl2 (1 mL) and
reprecipitated by adding MeOH (20 mL). This procedure was repeated
two to three times and the solid was collected to afford polymer 2.
Polymer 2a: Yield 92%; 1H NMR (500 MHz, CDCl3): d=0.7–0.9 (br,
9H; CH3), 0.9–1.7 (br, 44H; CH2), 1.7–2.2 (br, 6H; CH2), 2.2–2.5 (br,
6H; CH2), 2.5–3.0 (br, 4H), 3.0–3.9 (br, 8H), 4.2–4.7 (br, 2H), 4.9–5.6
(br, 2H), 6.1–6.8 (br, 2H), 7.5–7.8 (br, 2H), 7.8–8.1 (br, 2H), 8.1–8.6 (br,
8H), 8.7–9.0 ppm (br, 2H); 13C NMR (125 MHz, CDCl3): d=14.1, 22.7,
29.4, 29.8, 30.7, 30.9, 32.0, 34.4, 35.7, 38.7, 44.4, 46.2, 49.6, 111.7, 116.6,
117.3, 118.6, 119.3, 119.9, 126.1, 127.4, 131.0, 132.2, 135.4, 139.8, 148.0,
150.9, 151.3, 165.6 ppm; IR (KBr): n˜ =3123, 2949, 2923, 2852, 1725, 1606,
1557, 1527, 1500, 1479, 1466, 1379, 1270, 1205, 1177, 1165, 1061, 1009,
963, 825, 788 cmÀ1; GPC (THF): Mn =18865, Mw =20352, PDI=1.08.
4-Cyclohexyl-4-aza-tricyclo[5.2.1.02,6]dec-8-ene (12b): Compound 12a[26]
(0.50 g, 2.04 mmol) in THF (20 mL) was added slowly to a slurry of
LiAlH4 (0.33 g, 8.68 mmol) in THF (30 mL), and the mixture was re-
fluxed for 4 h. Water (3 mL) and NaOH (10%, 1 mL) were then added
and the resulting suspension was filtered. The residue was triturated with
THF repeatedly and filtered. The organic solution was dried (MgSO4)
and filtered, then the filtrate was evaporated in vacuo to give 12b as a
1
liquid (0.41 g, 93%). H NMR (400 MHz, CDCl3): d=1.08–1.22 (m, 6H),
1.58–1.78 (m, 2H), 2.79 (s, 2H), 2.88–2.92 (m, 2H), 3.01–3.05 ppm (m,
3H), 6.10 (s, 2H); 13C NMR (100 MHz, CDCl3): d=25.2, 26.1, 31.8, 44.7,
46.1, 53.9, 54.4, 63.6, 137.3 ppm; IR (KBr): n˜ =3059, 2958, 2929, 2853,
2796, 2772, 1636, 1449, 1346, 1136, 878, 799, 733, 714, 689, 465 cmÀ1
;
HRMS (FAB): m/z calcd for C15H24N: 218.1909 [M++H]; found:
218.1904.
Polymer 2b: Yield 91%; 1H NMR (400 MHz, CDCl3): d=0.7–0.9 (br,
9H; CH3), 0.9–1.5 (br, 42H; CH2), 1.5–1.9 (br, 8H; CH2; CH on norbor-
nene), 1.9–2.3 (br, 6H; CH2), 2.3–3.3 (br, 8H; H on norbornene), 3.8–4.5
(br, 8H; CH2), 4.8–5.4 (br, 2H; OCH2), 5.4–5.8 (br, 2H,), 6.1–6.6 (br,
2H; ArH), 7.5–7.7 (br, 2H; ArH), 7.7–8.2 (br, 4H; ArH), 8.2–8.9 ppm
(br, 8H; b-H); 13C NMR (100 MHz, CDCl3): d=14.3, 22.8, 29.5, 29.8,
29.9, 30.8, 32.0, 35.0, 38.9, 44.3, 46.3, 49.4, 65.9, 111.4, 117.6, 118.9, 119.2,
125.7, 127.6, 131.3, 134.3, 135.4, 142.5, 147.8, 148.1, 148.5, 150.6,
166.6 ppm; IR (KBr): n˜ =3123, 2952, 2922, 2852, 1707, 1606, 1522, 1466,
1375, 1271, 1179, 1008, 788 cmÀ1; GPC (THF): Mn =17136, Mw =20556,
PDI=1.19.
Polymer 2c: Yield 90%; 1H NMR (500 MHz, CDCl3): d=0.7–0.9 (br,
9H), 0.9–1.6 (br, 44H), 1.6–1.8 (br, 6H), 2.1–2.5 (br, 8H), 2.6–3.3 (br,
8H), 3.9–4.6 (br, 8H), 4.7–5.3 (br, 2H), 6.1–6.5 (br, 2H), 7.4–7.6 (br,
2H), 7.7–8.1 (br, 4H), 8.5–9.1 ppm (br, 8H, b-H); 13C NMR (125 MHz,
CDCl3): d=14.1, 22.7, 29.4, 29.7, 29.8, 30.7, 31.9, 32.4, 35.0, 38.8, 44.3,
46.2, 49.2, 63.7, 111.4, 117.3, 118.3, 119.1, 126.4, 127.8, 131.3, 134.5, 140.2,
140.7, 147.9, 148.4, 148.9, 150.8, 167.0 ppm; IR (KBr): n˜ =3018, 2952,
2923, 2852, 1705, 1606, 1523, 1466, 1377, 1273, 1180, 1104, 1077, 1007,
964, 788, 768, 707 cmÀ1; GPC (THF): Mn =15322, Mw =17275, PDI=
1.13.
Polymer 13: A solution of 12b (100 mg, 0.5 mmol) and (Cy3P)2Cl2Ru=
CHPh (18 mg, 0.05 equiv) in CH2Cl2 (5 mL) was stirred at RT under
argon for 30 min, quenched with ethyl vinyl ether (1 mL), and poured
into MeOH (20 mL). The solid was collected and dissolved in CHCl3
(1 mL) and reprecipitated by adding MeOH (20 mL). This procedure was
repeated three times and the solid was collected to afford 13 as a grayish
1
solid (81 mg, 81%). H NMR (400 MHz, CDCl3): d=1.21 (br, 2H), 1.40–
2.60 (br, 12H), 2.56–5.91 (br, 7H), 5.40 (br, for cis double bond, 21%),
5.48 ppm (br, for trans double bond, 79%); 13C NMR (100 MHz, CDCl3):
d=25.2, 26.2, 29.8, 32.1, 34.7, 36.3, 40.3, 44.8, 45.0, 45.8, 46.6, 54.4, 63.6,
63.7, 130.4 ppm and residual signals for end groups. IR (KBr): n˜ =3040,
2926, 2851, 2773, 1632, 1448, 1372, 1135, 969, 890, 691 cmÀ1; End-group
analysis showed that polymer 13 contained 27 repetitive units.
Time-resolved fluorescence experiments:
A mode-locked Ti:sapphire
laser (wavelength 850 nm, repetition rate 76 MHz, pulse width <200 fs)
was passed through an optical parametric amplifier to produce a l=
425 nm pulse laser. The fluorescence of the sample was reflected by a
grating (150 gmmÀ1, BLZ 500 nm) and detected by an optically triggered
streak camera (Hamamatsu C5680) with
a time resolution of about
0.3 ps. Each 1ꢂ10À5 m sample was prepared in CH2Cl2 and placed in an
ultra-micro cuvet with 1 mm pathlength to maintain simultaneous excita-
Chem. Eur. J. 2009, 15, 5719 – 5728
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5727

T.-Y. Luh et al.
tion. The signal was collected twenty times to decrease signal-to-noise
ratio [A1exp (Àt/t2)].
(Àt/t1)+A2exp
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Taipei, and Shanghai Institute of Organic Chemistry, Shanghai, for sup-
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Published online: April 22, 2009
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