106
S. Sakthivel et al. / Tetrahedron: Asymmetry 23 (2012) 101–107
and concentrated under reduced pressure and purified by flash chro-
matography to afford 3 as an orange solid in 22% (122.2 mg) yield.
Mp 102 °C; 1H NMR (400 MHz, CDCl3) d 11.06 (s, 2H), 9.88 (s, 2H),
7.53 (d, J = 8.0 Hz, 2H), 7.15–7.13 (m, 4H), 7.01 (s, 2H), 4.03 (t,
J = 6.4 Hz, 4H), 1.88–1.81 (m, 4H), 1.57–1.53 (m, 4H), 1.38–1.25
(m, 16 H), 0.87–0.84 (m, 6H); 13C NMR (100 MHz, CDCl3) d 195.9,
161.5, 154.2, 133.6, 132.2, 123.2, 120.4, 120.2, 117.1, 114.1, 94.3,
90.7, 69.8, 32.0, 29.6, 26.3, 22.8, 14.2; FT-IR (KBr) 3435, 2923,
2853, 2211, 1648, 1622, 1491, 1323, 1261, 1215, 1106, 973, 804,
744, 542 cmꢀ1. Anal. Calcd for C40H46O6: C, 77.14; H, 7.44; Found.
C, 77.22; H, 7.47.
4.6.2. Zinc titration
The solutions of the polymer 1b (3 mL, 1 ꢂ 10ꢀ5 M in THF with
respect to the monomeric unit) and zinc nitrate salt (9.0 ꢂ 10ꢀ4
M
in water) were thoroughly mixed at ambient temperature to
produce the corresponding Zn(II)-polymer 1b complex (Figure 5).
After 5 min, the fluorescent properties of the solution having the
in situ generated Zn(II)-polymer 1b complex were measured.
4.6.3. Pyridine titration
To the solutions of the Zn(II)-polymer complex (3 mL,
1 ꢂ 10ꢀ5 M in THF with respect to the monomeric unit, Zn2+ and
polymer ratio was 3:1), derived from Zn(NO3)2 (9.0 ꢂ 10ꢀ4 M in
water, 1 equiv) and 1b (3 mL, 1 ꢂ 10ꢀ5 M in THF with respect to
the monomeric unit) for 1 h, was added the solutions of pyridine
in THF (3.0 ꢂ 10ꢀ3 M in THF, 1–16 equiv). The resulting solutions
were mixed thoroughly. After 5 min, the fluorescence of the
respective solutions was measured (Fig. 8).
4.5. Synthesis of polymers 1a–b
4.5.1. Polymer 1a
To a stirred solution of the dialdehyde 3 (0.08 mmol, 50 mg) in
CHCl3 (3 mL), (1R,2R)-1,2-diaminocyclohexane 2a (0.080 mmol,
9.12 mg) was added and the resulting solution was heated at
45 °C for 3 h. The reaction mixture was then cooled to room tem-
perature, concentrated (ca. 2 mL) and treated with MeOH (3 mL).
The resultant precipitate 1a was collected by filtration as a yellow
powder in a 78% (43.80 mg) yield. GPC: Mw = 12102, Mn = 9513
(PDI 1.27); 1H NMR (400 MHz, CDCl3) d 8.21 (s, 2H), 7.09 (d,
J = 7.6, 2H), 7.02 (s, 2H), 6.97–6.92 (m, 4H), 3.96 (t, J = 6.4 Hz, 4H),
3.28 (s, 2H), 1.91–1.60 (m, 16H), 1.47–1.45 (m, 6H), 1.31–1.22 (m,
10H), 0.80 (m, 6H); 13C NMR (100 MHz, CDCl3) d 164.4, 160.9,
153.9, 131.4, 127.3, 122.2, 119.7, 118.7, 117.1, 114.1, 94.9, 88.0,
72.7, 69.8, 33.2, 31.9, 29.4, 26.2, 24.3, 22.8, 14.3; FT-IR (KBr) 3463,
2961, 2928, 2862, 2373, 2071, 1629, 1462, 1262, 1215, 1091,
Acknowledgments
This work was supported by the Department of Science and
Technology, New Delhi, and Council of Scientific and Industrial
Research, New Delhi. We thank Professor T. Katsuki Kyushu
University for CD analysis.
References
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the Novel Science and Technology of Highly Conducting and Nonlinear Optically
Active Materials; Kluwer Academic Publishers: Boston, 1991; (d) Kiess, H. G.
Conjugated Conducting Polymers; Springer-Verlag: New York, 1992; (e) Miyata,
S.; Nalwa, H. S. In Organic Electroluminescent Material and Devices; Gordon and
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1028, 801, 697 cmꢀ1; UV–vis (THF): k
(e) = 320 (42325), 382
max
(57713) nm (Mꢀ1 cmꢀ1); fluorescence (kex = 380 nm, THF):
502 nm; ½a 2D0
¼ ꢀ797 (c 0.1, CHCl3). Anal. Calcd for (C46H56N2O4)n:
ꢄ
C, 78.82; H, 8.05; N, 4.00. Found: C, 78.88; H, 8.07; N, 4.05.
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4.5.2. Polymer 1b
To a stirred solution of the dialdehyde 3 (0.08 mmol, 50 mg) in
CHCl3
(3 mL),
(1R,2R)-1,2-diphenylethylene-diamine
2b
(0.080 mmol, 16.90 mg) was added and the resulting solution
was heated at 45 °C for 3 h. The reaction mixture was then cooled
to room temperature, concentrated (ca. 2 mL) and treated drop-
wise with MeOH (3 mL). Isolation of 1b was performed as de-
scribed for 1a as a yellow powder in a 76% (48.76 mg) yield.
GPC: Mw = 22157, Mn = 14853 (PDI 1.49); 1H NMR (400 MHz,
CDCl3) d 8.26 (s, 2H), 7.18–6.93 (m, 18H), 4.71 (s, 2H), 3.97 (t,
J = 6.4 Hz, 4H), 1.80 (t, J = 6.8 Hz, 4H), 1.59–1.47 (m, 8H), 1.23 (s,
12H), 0.81 (s, 6H); 13C NMR (100 MHz, CDCl3) d 165.8, 160.8,
153.9, 139.3, 131.7, 128.6, 128.0, 127.7, 122.3, 119.8, 118.6,
117.1, 114.1, 94.8, 88.3, 80.4, 69.8, 31.9, 29.5, 26.2, 22.8, 14.3;
FT-IR (KBr) 3452, 2961, 2923, 2857, 2362, 2093, 1627, 1377,
1262, 1212, 1102, 1023, 973, 697 cmꢀ1
; UV-vis (THF): kmax
(e
) = 322 (36461), 381 (50261) nm (Mꢀ1 cmꢀ1); fluorescence
(kex = 380 nm, THF): 503 nm; ½a D20
ꢄ
= -244 (c 0.1, CHCl3). Anal. Calcd
for (C54H58N2O4)n: C, 81.17; H, 7.32; N, 3.51. Found: C, 81.25; H,
7.33; N, 3.55.
4.6. Fluorometric titration
10. (a) Harada, N.; Nakanishi, K. Circular Dichroic Spectroscopy; Oxford University
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1975, 3165.
4.6.1. Metal ion titration
The solutions of the polymers 1a–b (3 mL, 1 ꢂ 10ꢀ5 M in THF
with respect to the monomeric unit) and metal nitrate salts
(3.0 ꢂ 10ꢀ4 M in water, 1 equiv) were thoroughly mixed at ambi-
ent temperature to produce the corresponding metal-polymer
complexes (Fig. 4). After 5 min, the fluorescent properties of the
solution having the in situ generated metal–polymer 1a–b com-
plexes were measured.
11. For examples, see: (a) McQuade, D. T.; Pullen, A. E.; Swager, T. M. Chem. Rev.
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´
12. (a) Pina, F.; Bernardo, M. A.; Garcla-Espana, E. Eur. J. Inorg. Chem. 2000, 2143;
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