Synthesis of metallo-supramolecular polymers using 5,5′-linked bis(1,10-phenanthroline) ligands

Article abstract of DOI:10.1055/s-0032-1316858

5,5′-Linked bis(1,10-phenanthroline)s were synthesized as new bidentate ligands by a palladium-catalyzed Suzuki-type cross-coupling reaction. Coordination of the ligands to Cu(II), Ni(II), Ag(I), and Zn(II) ions resulted in metallo-supramolecular polymer formation. The 1:1 complexation of the ligands and the metal ions was confirmed by UV-vis titration experiments. The high molecular weights of more than 10⁵ Da, caused by the high complexation constants, were confirmed by the SEC-Viscometry-RALLS method. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0032-1316858

PAPER
▌753
pSapyenr thesis of Metallo-Supramolecular Polymers Using 5,5′-Linked
Bis(1,10-Phenanthroline) Ligands
Synthesis of Metallo-Supramolecular Polymers
a
a,b
Md. Delwar Hossain, Masayoshi Higuchi*
a
Electronic Functional Materials Group, Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki,
Tsukuba 305-0044, Japan
b
JST-CREST, Japan
Fax +81(29)8604721; E-mail: HIGUCHI.Masayoshi@nims.go.jp
Received: 25.12.2012; Accepted after revision: 31.01.2013
6
tion. Compound 1 was synthesized in the same manner as
Abstract: 5,5′-Linked bis(1,10-phenanthroline)s were synthesized
as new bidentate ligands by a palladium-catalyzed Suzuki-type
cross-coupling reaction. Coordination of the ligands to Cu(II),
a previously reported procedure (Scheme S1 in the Sup-
7
porting Information). The reaction of 1 (0.8 mmol) with
Ni(II), Ag(I), and Zn(II) ions resulted in metallo-supramolecular 3 (0.4 mmol) was carried out in the presence of
polymer formation. The 1:1 complexation of the ligands and the PdCl (PPh ) (5 mol%) and potassium carbonate (2.4
2
3 2
metal ions was confirmed by UV-vis titration experiments. The mmol) in anhydrous dimethyl sulfoxide (30 mL) at 100 °C
5
high molecular weights of more than 10 Da, caused by the high
for 24 hours under a nitrogen atmosphere. Purification of
complexation constants, were confirmed by the SEC-Viscometry-
the reaction mixture by alumina column chromatography
RALLS method.
and preparative HPLC gave the dimerized product L1 in
Key words: bis(1,10-phenanthroline)s,
polymers, complexation, cross-coupling, palladium
metallo-supramolecular
7
5% yield (Table 1, entry 1). Pd(PPh ) was also effective
3 4
and gave L1 in 65% (entry 2). Since PdCl (PPh ) was
2
3 2
easier to handle and more stable to moisture than
Pd(PPh ) , we chose PdCl (PPh ) for the later optimiza-
3
4
2
3 2
During the last few decades, metallo-supramolecular
polymers, which are synthesized via complexation of met-
al ions with bidentate organic ligands, have received
much attention due to their potential and wide applica-
tion. When potassium carbonate was replaced with potas-
sium acetate, the yield of L1 was lower due to its
decreased basicity (entry 3). The use of dioxane or tetra-
hydrofuran as the solvent resulted in low yields of L1 be-
cause of the extremely poor solubility of L1 (entries 4 and
1
a,b
tions, including information storage,
electrochromic
1
c–g
1h
1i
displays,
sensors, self-healing, stimuli-responsive
5
). Increasing the amount of catalyst PdCl (PPh ) from 5
2 3 2
gels,1j and emissive materials. Various N-heteroaro-
matic compounds such as bis(terpyridine)s, bis(bipyri-
dine)s, and bis(porphyrin)s have been reported as the
1k,l
to 10 mol% did not improve the final yield of L1, the yield
decreased due to the formation of a complex as a byprod-
uct instead of the desired product (entry 6). Using the con-
ditions in entry 1 and scaling up the reaction 10 times to 8
mmol of 1 gave L1 in almost the same yield (72%) (entry
1
bidentate ligands in metallo-supramolecular polymers.
1,10-Phenanthroline is also useful ligand for metal ions
with a tetrahedral or square planar coordination structure
such as zinc(II), copper(II), gold(III), and platinum(II),
but reports on bidentate 1,10-phenanthroline ligands are
7).
The methodology was extended to the synthesis of
bis(1,10-phenanthroline) L2 having methyl groups in the
phenanthroline moieties (Scheme 1); L2 was prepared
from 5-bromoneocuproine (2) in the same manner as L1.
Compound 2 was prepared using several steps according
to the literature method (Scheme S1 in the Supporting In-
2
,3
limited to 2,2′-linked bis(1,10-phenanthroline)s. It is
considered that 5,5′-linked bis(1,10-phenanthroline)s are
more suitable to form linear metallo-supramolecular poly-
4
mers than 2,2′-linked ones due to lower steric hindrance.
Very recently we reported a 5,5′-linked bis(1,10-phenan-
8
formation). 5,5′-Linked bis(1,10-phenanthroline)s with a
throline) ligand and the corresponding copper(II)-based
5
5
fluorene moiety as a spacer L3 and L4 were obtained us-
metallo-supramolecular polymer. We herein report the
ing 9,9-dioctyl-9H-fluorene-2,7-diboronic acid bis(pro-
pane-1,3-diol) ester (4). The obtained fluorene derivatives
were found to be very stable and they had good solubility
in all common organic solvents. Two 2,9-dimethyl-1,10-
phenanthrolines (i.e., from 5-bromoneocuproine) were
connected directly (without spacer) at the 5-position by
treatment of 2 with bis(pinacolato)diboron (5) for 16
hours at 80 °C to give 5,5′-bis(2,9-dimethyl-1,10-phenan-
throline) (L5). The new ligands L1, L2, L4, and L5 were
purified by column chromatography and characterized by
synthesis of new 5,5′-linked bis(1,10-phenanthroline) li-
gands and the corresponding metallo-supramolecular
polymers bearing copper(II), nickel(II), silver(I), or
zinc(II).
A 5,5′-linked bis(1,10-phenanthroline) with a phenyl
group as the spacer L1 was synthesized from 5-bromo-
1,10-phenanthroline (1) and 1,4-benzenediboronic acid
bis(pinacol) ester (3) by Suzuki-type cross-coupling reac-
1
13
SYNTHESIS 2013, 45, 0753–0758
H and C NMR (Figures S1–S8 in the Supporting Infor-
Advanced online publication: 14.02.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
mation) and high resolution mass spectrometry (HRMS).
DOI: 10.1055/s-0032-1316858; Art ID: SS-2012-F0995-OP
Georg Thieme Verlag Stuttgart · New York
Characterization data of L3 were reported in our recent
©
5
paper.

754
M. D. Hossain, M. Higuchi
PAPER
Table 1 Synthesis of L1 by Suzuki Coupling Reaction of 5-Bromophenanthroline (1) with 1,4-Benzenediboronic Acid Bis(pinacol) Ester (3)
under Different Conditionsa
O
O
O
O
B
B
N
N
N
3
N
N
catalyst, base, solvent
65–100 °C, 24–30 h
Br
N
1
L1
Entry
Catalyst
Base
Solvent
Temp (°C)
Yield (%)
1
2
3
4
5
6
PdCl (PPh )
K CO
DMSO
DMSO
DMSO
100
100
100
100
65
75
65
40
10
30
70
72
2
3
2
2
3
Pd(PPh3)4
K CO
2
3
PdCl (PPh )
KOAc
K CO
2
3
2
2
2
2
2
PdCl (PPh )
1,4-dioxane
THF
2
3
2
3
PdCl (PPh )
K CO
2
3
2
3
3
3
b
c
PdCl (PPh )
K CO
DMSO
DMSO
100
100
2
3
2
7
PdCl (PPh )
K CO
2
3
2
a
Conditions for entries 1–5: 1 (0.2 g, 0.8 mmol), 3 (0.5 equiv), catalyst (5 mol%), base (3 equiv), solvent (30 mL), 24 h.
Catalyst (10 mol%).
Conditions: 1 (2.0 g, 8.0 mmol), 3 (0.5 equiv), catalyst (5 mol%), base (3 equiv), DMSO (250 mL), 30 h.
b
c
O
O
O
O
B
B
N
3
N
N
PdCl2(PPh3)2, K2CO3
DMSO, 100 °C, 24 h
N
L2 (70%)
C8H17 C H
8
17
R
N
R
R
O
O
O
B
B
C H
C H
8
17
8
17
N
N
O
R
4
N
N
PdCl2(PPh3)2, K2CO3
DMSO, 100 °C, 24 h
R
Br
N
R
L3: R = H (35%)
L4: R = Me (60%)
1
2
: R = H
: R = Me
O
O
O
O
B
B
N
5
N
N
PdCl2(PPh3)2, K2CO3
DMSO, 80 °C, 16 h
N
L5 (78%)
Scheme 1 Synthesis of 5,5′-linked bis(1,10-phenanthroline)s L2–L5
Synthesis 2013, 45, 753–758
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Metallo-Supramolecular Polymers
755
Among various combinations of ligands L1–L5 and metal change observed after the addition of 1.1–2.0 equivalents
ions with a tetrahedral (or square planer) coordination of copper(II) salt. The stoichiometry between the metal
structure, we investigated five combinations of Cu(II)– ions and the ligand in the polymer formation could be con-
L1, Ni(II)–L2, Ag(I)–L3, Zn(II)–L4, and Zn(II)–L5 to firmed by plots between the absorbance at 290 nm and the
confirm the utility of the new ligands for the synthesis of molar ratio (metal/ligand) [Figure 1 (a) inset]. The inten-
versatile metallo-supramolecular polymers. Metallo-su- sity of the band at 290 nm increased in proportional to the
pramolecular polymers, CuL1, NiL2, AgL3, ZnL4, and molar ratio, and then reached saturation at around 1.0.
ZnL5, were obtained by mixing equimolar amounts of the These experiments clearly showed that coordination oc-
ligands and metal ions in anhydrous acetonitrile–dichlo- curred in a 1:1 stoichiometric ratio of metal [Cu(II) salt]
romethane for several hours under a nitrogen atmosphere to ligand L1 in CuL1 and such sharp change of the absor-
at room temperature (Scheme 2). The complexation was bance at the 1:1 ratio suggests that the complexation con-
7
confirmed by a color change during the reactions. The de- stant is very high (more than 10 ). Similarly, the
sired polymers were isolated in 89–96% yields. All poly- spectrophotometric titration were employed for L2–L5
mers showed good solubility to acetonitrile. The polymer with metal salts Ni(II), Ag(I), and Zn(II) [Figure 1 (b)–
structures will have a syn form as well as an anti form at (e)] and the relationship between the absorbance and the
the metal complex moieties, as shown in Scheme 2, due to molar ratio (metal/ligand) was plotted in each case [Figure
rotation around the carbon–carbon bond between the 1 (b) inset to (e) inset]. In all cases coordination reached
complex moiety and the spacer in the ligands.
the saturation point at a 1:1 ratio of metal to ligand, which
indicated polymer formation.
The 1:1 complexation of the ligand and the metal ion in
the polymer formation was supported by titration experi- Molecular weight (Mw) of the polymers (CuL1
5
5
ments of the metal ion with the ligand solution in the UV- Mw = 1.22 × 10 Da, NiL2 Mw = 1.59 × 10 Da, AgL3
5
5
vis spectra (Figure 1). Figure 1 (a) shows UV-vis spectral Mw = 1.32 × 10 Da, ZnL4 Mw = 1.19 × 10 Da, and
5
change by the titration of copper(II) ions with a L1 solu- ZnL5 Mw = 1.01 × 10 Da) was determined using the
tion: during the addition of Cu(ClO ) ·6 H O, an absorp- SEC-Viscometry-RALLS method with polyethylene ox-
4
2
2
tion around 310 nm, based on π–π* transition of the ide Std (Figures S9–S13 in the Supporting Information)
phenanthroline units shifted to a longer wavelength with acetonitrile as the solvent.
9
(λmax = 321.5 nm) by complexation with copper(II) ions.
In conclusion, we have demonstrated a quick, simple, and
efficient method for the synthesis of 5,5′-linked bis(1,10-
phenanthroline)s via Suzuki-type cross-couplings. New
The spectral change occurred during the addition of 0.0–
1.0 equivalents of copper(II) salt and there is no spectral
R
N
R
R
N
N
M
N
R
Cu(II) or Ni(II)
N
N
N
R
R
CH2Cl2–MeCN
r.t., N2 atm, 3 h
R
N
R
n
L1: R = H
L2: R = Me
CuL1: M = Cu(II) R = H (90%)
NiL2: M = Ni(II) R = Me (95%)
R
N
R
R
N
N
C8H17
C8H17
C8H17
C8H17
M
N
R
Ag(I) or Zn(II)
N
N
N
R
R
CH2Cl2–MeCN
r.t., N2 atm, 1 h
R
N
R
n
L3: R = H
L4: R = Me
AgL3: M = Ag(I) R = H (89%)
ZnL4: M = Zn(II) R = Me (94%)
N
N
N
Zn
N
Zn(II)
N
N
N
CH2Cl2–MeCN
r.t., N2 atm, 2 h
N
n
L5
ZnL5 (96%)
Scheme 2 Preparation of metallo-supramolecular polymers CuL1, NiL2, AgL3, ZnL4, and ZnL5
©
Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 753–758

756
M. D. Hossain, M. Higuchi
PAPER
(
a)
(b)
0.0
0.5
1.0
1.5
2.0
0.0
0.5
1.0
1.5
[
metal]/[Ligand]
[metal]/[Ligand]
1
.1–2.0 equiv
1.11–1.44 equiv
0.11–1.0 equiv
0.0 equiv
0
.1–1.0 equiv
0.0 equiv
280
350
420
490
280
350
wavelength (nm)
420
490
wavelength (nm)
(
c)
(d)
0.0
0.5
1.0
1.5
0.0
1.5
0
.5
1.0
[
metal]/[Ligand]
[metal]/[Ligand]
1
0
.125–1.625 equiv
.125–1.0 equiv
.0 equiv
1.11–1.44 equiv
0.11–1.0 equiv
0.0 equiv
0
280
350
wavelength (nm)
420
490
280
350
wavelength (nm)
420
490
(
e)
0.0
0.5
1.0
1.5
[
metal]/[Ligand]
1
0
.1–1.4 equiv
.1–1.0 equiv
0.0 equiv
280
350
wavelength (nm)
420
490
Figure 1 UV-vis spectral changes in the titration of (a) Cu(ClO ) ·6 H O, (b) Ni(ClO ) ·6 H O, (c) AgBF , (d) and (e) Zn(ClO ) ·6 H O solu-
4
2
2
4
2
2
4
4
2
2
-4
-5
tions (MeCN, c = 5 × 10 M) with (a) L1, (b) L2, (c) L3 (d) L4, and (e) L5 solutions (CH Cl , c = 1.0 × 10 M, l = 1 cm) at r.t. The inset shows
2
2
the change in absorbance at (a) 290 nm, (b) 297 nm, (c) 379 nm, (d) 307.4 nm, and (e) 304.4 nm as a function of the corresponding added metal
salt.
copper(II)-, nickel(II)-, silver(I)-, and zinc(II)-based 1H and 13C NMR spectra were recorded at 300 and 75 MHz, respec-
tively, on a Jeol AL 300/BZ instrument with TMS as an internal
standard. Mass spectra were measured by using an AXIMA-CFR,
Shimadzu/Kratos TOF Mass spectrometer. HRMS were measured
by using a Shimadzu LCMS-IT-TOF spectrometer.
metallo-supramolecular polymers were successfully syn-
thesized by simple complexation of the ligands with cop-
per(II), nickel(II), silver(I), and zinc(II) salts. The
spectrophotometric titration experiments supported 1:1
complexation of the ligand with the metal ion, as well as
the high binding constants. The formation of the high-
molecular-weight polymers was confirmed by the SEC-
Viscometry-RALLS method. Details on the electrochem-
Bis(phenanthroline)s L1–L5; General Procedure
To a soln of phenanthroline 1 or 2 (0.8 mmol) in DMSO (30 mL)
was sequentially added diboronic ester 3, 4, or 5 (0.40 mmol),
K CO (2.4 mmol), and PdCl (PPh ) (5 mol%). The soln was de-
2
3
2
3 2
gassed and stirred 100 °C under N for 16–24 h. When the reaction
2
ical and photophysical properties of the obtained poly- was complete, DMSO was removed under reduced pressure at 115
°
C. The mixture was cooled to r.t. and CHCl (50 mL) was added.
mers are now under investigation.
3
Synthesis 2013, 45, 753–758
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of Metallo-Supramolecular Polymers
757
The catalyst was removed by filtration and washed thoroughly with
CHCl . The filtrate was then washed with H O (3 × ca. 50 mL). The
and this was rinsed thoroughly with Et O (20 mL), filtered off, and
dried in vacuo at r.t. to afford the desired polymer CuL1, NiL2,
2
3
2
organic layer was separated, dried (Na SO ), filtered, concentrated,
AgL3, ZnL4, or ZnL5.
2
4
and purified by HPLC (CHCl ) then finally column chromatogra-
3
CuL1
phy (activated basic Al O ) to give the desired product L1–L5.
2
3
5
Green solid; yield: 90%; Mw: 1.22 × 10 Da.
5
-[4-(1,10-Phenanthrolin-5-yl)phenyl]-1,10-phenanthroline
IR (KBr): 2922, 2855, 1721, 1542, 1528, 1462, 1431, 1012 (strong
peak, uncoordinated perchlorate anion), 893, 738, 625 cm .
(L1)
–1
White solid; yield: 0.13 g (75%); mp >300 °C.
1
H NMR (300 MHz, CDCl ): δ = 9.26 (m, 4 H), 8.45 (dd, J = 1.8,
NiL2
3
5
Light pink solid; yield: 95%; Mw: 1.59 × 10 Da.
1.8 Hz, 2 H), 8.32 (dd, J = 1.8, 1.8 Hz, 2 H), 7.88 (s, 2 H), 7.75 (s,
4
H), 7.73–7.65 (m, 4 H).
IR (KBr): 2928, 2856, 1619, 1467, 1428, 1382, 1103 (strong peak,
uncoordinated perchlorate anion), 890, 838, 810, 739, 625 cm .
–1
13
C NMR (75 MHz, CDCl ): δ = 150.5, 150.3, 146.6, 146.0, 138.8,
3
1
38.3, 136.0, 134.4, 130.3, 128.2, 127.8, 126.8, 123.5, 122.9.
AgL3
MS (MALDI-TOF): m/z (%): 434.89 (100) [M+].
5
Brown solid; yield: 89%; Mw: 1.32 × 10 Da.
+
HRMS (ESI): m/z [M + H] calcd for C H N : 435.1604; found:
IR (KBr): 3066, 1597, 1545, 1423, 1277, 1233, 938, 844, 725, 612
cm .
3
0
19
4
–1
435.1595.
2
,9-Dimethyl-5-[4-(2,9-dimethyl-1,10-phenanthrolin-5-yl)phe-
ZnL4
5
nyl]-1,10-phenanthroline (L2)
White solid; yield: 94%; Mw: 1.19 × 10 Da.
Brown solid; yield: 0.14 g (70%); mp >300 °C.
IR (KBr): 2925, 2849, 1697, 1617, 1559, 1520, 1455, 1430, 1105
(strong peak, uncoordinated perchlorate anion), 890, 832, 736, 621
1
H NMR (300 MHz, CDCl ): δ = 8.29 (d, J = 8.4 Hz, 2 H), 8.15 (d,
3
J = 8.4 Hz, 2 H), 7.76 (s, 2 H), 7.69 (s, 4 H), 7.50 (q, J = 8.1, 8.4 Hz,
4
–1
cm .
H), 2.98 (s, 12 H).
1
3
ZnL5
C NMR (75 MHz, CDCl ): δ = 159.6, 159.3, 145.9, 145.2, 139.1,
3
5
White solid; yield: 96%; Mw: 1.01 × 10 Da.
1
2
37.4, 136.3, 134.6, 130.3, 126.4, 126.0, 125.8, 123.9, 123.3, 26.0,
5.8.
IR (KBr): 2926, 2854, 1592, 1496, 1422, 1367, 1289, 1086, (strong
peak, uncoordinated perchlorate anion), 893, 832, 747, 686, 620
MS (MALDI-TOF): m/z (%): 490.02 (100) [M+].
–
1
cm .
+
HRMS (ESI): m/z [M + H] calcd for C H N : 491.2230; found:
3
4
27
4
4
91.2204.
Acknowledgment
2
,9-Dimethyl-5-[8-(2,9-dimethyl-1,10-phenanthrolin-5-yl)-9,9-
dioctylfluoren-2-yl]-1,10-phenanthroline (L4)
This work was financially supported by the Ministry of Education,
Culture, Sports, Sciences, and Technology, Japan (MEXT) and the
Japan Science and Technology Agency (JST).
Light orange solid; yield: 0.19 g (60%); mp 133–134 °C.
1
H NMR (300 MHz, CDCl ): δ = 8.25–8.17 (m, 4 H), 7.93 (d,
3
J = 7.5 Hz, 2 H), 7.76 (s, 2 H), 7.57–7.54 (m, 6 H), 7.45 (d, J = 8.4
Hz, 2 H), 2.99 (m, 12 H), 2.1–2.0 (m, 4 H), 1.14 (m, 20 H), 0.85–
Supporting Information for this article is available online at
0.78 (m, 10 H).
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
m
tgioSrantnugIifoop
r
itmnatr
13
C NMR (75 MHz, CDCl ): δ = 159.3, 159.1, 151.3, 145.6, 144.8,
3
1
1
2
40.4, 138.3, 138.2, 136.3, 134.8, 129.0, 126.3, 126.2, 125.5, 125.4,
24.7, 123.9, 123.2, 120.0, 55.5, 40.3, 31.8, 30.0, 29.3, 29.2, 26.0, References
5.8, 24.1, 22.6, 14.1.
(
1) (a) Whittell, G. R.; Hager, M. D.; Schubert, U. S.; Manners,
I. Nat. Mater. 2010, 10, 176. (b) Bandyopadhyay, A.; Sahu,
S.; Higuchi, M. J. Am. Chem. Soc. 2011, 133, 1168. (c) Yu,
S.-C.; Kwok, C.-C.; Chan, W.-K.; Che, C.-M. Adv. Mater.
MS (MALDI-TOF): m/z (%): 803.02 (100) [M + H]+.
HRMS (ESI): m/z [M + Na]+ calcd for C H N Na: 825.4867;
5
7
62
4
found: 825.4848.
(
Weinheim, Ger.) 2003, 15, 1643. (d) Higuchi, M.; Kurth, D.
5
,5′-Bis(2,9-dimethyl-1,10-phenanthroline) (L5)
G. Chem. Rec. 2007, 7, 203. (e) Han, F. S.; Higuchi, M.;
Kurth, D. G. Adv. Mater. (Weinheim, Ger.) 2007, 19, 3928.
(f) Han, F. S.; Higuchi, M.; Kurth, D. G. J. Am. Chem. Soc.
2008, 130, 2074. (g) Higuchi, M. Polym. J. 2009, 41, 511.
(h) Wojtecki, R. I.; Meador, M. A.; Rowan, S. J. Nat. Mater.
2010, 10, 14. (i) Burnworth, M.; Tangl, L.; Kumpferl, J. R.;
Duncan, A. J.; Beyer, F. L.; Fiore, G. L.; Rowan, S. J.;
Weder, C. Nature (London) 2011, 472, 334. (j) Kwok, C.-C.;
Yu, S.-C.; Sham, I. H. T.; Che, C.-M. Chem. Commun. 2004,
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4947. (l) Ravindra, R. P.; Higuchi, M.; Negishi, Y.;
Light yellow solid; yield: 0.13 g (78%); mp >300 °C.
1
H NMR (300 MHz, CDCl ): δ = 8.16 (d, J = 8.1 Hz, 2 H), 7.82 (s,
3
2
H), 7.65 (d, J = 8.4 Hz, 2 H), 7.57 (d, J = 8.1 Hz, 2 H), 7.31 (d,
J = 8.4 Hz, 2 H), 3.01 (s, 6 H), 2.94 (s, 6 H).
13
C NMR (75 MHz, CDCl ): δ = 159.9, 159.6, 145.2, 145.1, 136.3,
3
134.8, 134.6, 127.0, 126.9, 126.2, 124.0, 123.6, 26.0, 25.8.
MS (MALDI-TOF): m/z (%): 415.03 (100) [M + H]+.
+
HRMS (ESI): m/z [M + H] calcd for C H N : 415.1917; found:
2
8
23
4
415.1902.
Tsukuda, T.; Kurth, D. G. Polym. J. 2010, 42, 336.
2) (a) Reed, J. E.; Neidle, S.; Vilar, R. Chem. Commun. 2007,
Metallo-Supramolecular Polymers CuL1, NiL2, AgL3, ZnL4,
and ZnL5; General Procedure
(
4366. (b) Reed, J. E.; White, A. J.; Neidle, S.; Vilar, R.
Under N , ligand L1, L2, L3, L4, or L5 (0.03 mmol) was dissolved
2
Dalton Trans. 2009, 2558. (c) Rajput, C.; Rutkaite, R.;
Swanson, L.; Haq, I.; Thomas, J. A. Chem. Eur. J. 2006, 12,
in CH Cl (5 mL). Then Cu(ClO ) ·6 H O, Ni(ClO ) ·6 H O,
2
2
4
2
2
4
2
2
AgBF , or Zn(ClO ) ·6 H O (0.03 mmol) dissolved in MeCN (5
4
4
2
2
4611. (d) Talib, J.; Green, C.; Davis, K. J.; Urathamakul, T.;
mL) was added dropwise over 30 min. The mixture was stirred for
–3 h at r.t. The solvent was slowly evaporated by leading a stream
of N over the mixture. During this procedure, a precipitate formed
Beck, J. L.; Aldrich-Wright, J. R.; Ralph, S. F. Dalton Trans.
1
2
008, 1018. (e) Hudson, Z. D.; Sanghvi, C. D.; Rhine, M. A.;
Synthesis 2013, 45, 753–758
2
©
Georg Thieme Verlag Stuttgart · New York

758
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