Supporting Information of
Ferromagnetic behavior of an aniline functionalized polyferrocenylsilane
complex
Hongding Tang and Yunyang Liu
Department of Chemistry, Wuhan University, Wuhan 430072, China.
Jingui Qin a)
Department of Chemistry, Wuhan University, Wuhan 430072, China and State Key
Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai 200032, China.
Makoto Inokuchi and Minoru Kinoshita
Faculty of Science and Engineering, Department of Materials Science and
Environmental Engineering, Tokyo University of Science, Yamaguchi, Onoda,
Yamaguchi 756-0884, Japan
a)
Author to whom the correspondence should be addressed; E-mail: jgqin@whu.edu.cn
Tel: 86-27-68764117 Fax: 86-27-87647617
Experimental
PFSs I and II were obtained by transition-metal catalyzed ring-opening
corresponding [1]silaferrocenophane prepared by treating 1,1’-dilithioferrocene with the
corresponding substituted dichlorosilanes.[9] The orange-yellow polymers were purified
by precipitating from THF/methanol twice. The average weight molecular weights (Mw)
were measured by gel permeation chromomatography (GPC) in THF with a reference of
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the monodispersed polystyrene standard. Electrochemical experiments were carried out
under N2 in CH2Cl2 solution of I and II and 0.1 M Bu4NPF6 using a CHI 660A
electrochemical workstation (CH instruments, Shanghai) and a Pt working electrode and
Ag/AgCl as reference electrode with a sweep rate of 100 mV/s.
I: 1H NMR(CDCl3): 7.1(br, 2H, Ar-H), 6.7(m, 2H, Ar-H), 4.1-3.7(m, br, 8H, Cp-H),
2.9(br, 6H, -N(CH3)2), 2.6(br, 2H, Ar-CH2-), 1.7(br, 2H, -C-CH2-C-), 0.9(br, 2H, Si-CH2C), 0.4(s, 3H, Si-CH3). FT-IR (KBr, cm-1): 3413, 3085, 2918, 2792, 1614, 1520, 1338,
1247, 1162, 1035, 809, 771, 486. Anal. Calcd. For (C22H27NFeSi)n: C, 67.87; H, 6.94; N,
3.60. Found: C, 67.83; H, 7.10; N, 3.30. Mw = 1.08 × 10 5, PDI = 1.91. Tg = 62 oC. Td =
402 oC. 1E1/2 = 0.462 V, 2E1/2 = 0.707 V (refer to Ag/AgCl).
II: 1H NMR(CDCl3): 7.2(br, 2H, Ar-H), 6.6(m, 3H, Ar-H), 4.2-4.0(m, br, 8H, Cp-H),
3.4-3.2(br, 4H, N-CH2-), 1.6(br, 2H, N-C-CH2-C-), 1.1(t, 3H, -C-CH3), 0.8(br, 2H, SiCH2-C), 0.5(s, 3H, Si-CH3). FT-IR (KBr, cm-1): 3431, 3089, 2962, 2926, 2870, 1594,
1502, 1359, 1247, 1160, 1032, 833, 772, 742, 685, 486. Anal. Calcd. For (C22H27NFeSi)n:
C, 67.87; H, 6.94; N, 3.60. Found: C, 67.68; H, 6.91; N, 3.54. Mw = 9.1 × 10 4, PDI =
3.01. Tg = 26 oC. Td = 350 oC. 1E1/2 = 0.459 V, 2E1/2 = 0.708 V (refer to Ag/AgCl).
The chemical oxidization was carried out in the CH2Cl2 solution by adding iodine
into polymers. After stirring at room temperature for additional 10 hrs, the precipitate
was collected and repeatedly washed with CH2Cl2 sufficiently till filtrate colorless, then
dried in vacuum to give oxidized products III and IV. Iron-57 Mössbauer spectroscopy
was performed on Oxford Ins. MS 500 Mössbauer instrument with Co/RT as the
radioactive source and intensity as 25 mC. Isomers were reported relative to iron metal.
Computer fittings of the data to Lorentenzian lines were carried out with X2 < 1.5. Solid-
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state magnetic properties were measured using a Quantum Design MPMS-5s SQUID
magnetometer. Data were corrected for the diamagnetism of the sample holder, by
extrapolation of χ vs 1/T to infinite temperature.
III: FT-IR (KBr, pellet): 3421, 3072, 2922, 2850, 1652, 1604, 1507, 1456, 1379,
1249, 1159, 1033, 831, 771. Anal. Calcd. For [I]nx+[I2.81x-] n. C, 35.4; H, 3.62; N, 1.88.
Found: C, 35.3; H, 4.19; N, 2.50. Mössbauer data: Fe(II), δ=0.45mm/s, Qs=2.27mm/s,
%=35%; Fe(III), δ=0.63mm/s, Qs=0.31mm/s, %=65%. θ=-9.0K, C=8.49 × 10-4 emu/g.
IV: FT-IR (KBr, pellet): 3438, 3080, 2932, 2871, 1637, 1593, 1483, 1439, 1379,
1252, 1158, 1032, 1004, 856, 833, 767, 685, 547, 470. Anal. Calcd. For [II]nx+[I6.06x-] n.
C, 22.1; H, 2.26; N, 1.17. Found: C, 22.1; H, 2.40; N, 1.20. Mössbauer data: Fe(II),
δ=0.26mm/s, Qs=2.33mm/s, %=36%; Fe(III), δ=0.28mm/s, Qs=0.31mm/s, %=64%. θ=1.3K, C=1.54 × 10-4 emu/g. θ=-1.3K, C=1.54 × 10-3 emu/g.
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-4
1.6x10
III
IV
-4
χ , emg g
-1
1.2x10
-5
8.0x10
-5
4.0x10
0.0
0
50
100
150
200
250
300
Temperature, T, K
Fig. S1. Magnetic susceptibility (χ-1) as a function of temperature (T) for III and IV.
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5
6x10
III
IV
5
5x10
5
5
3x10
-1
-1
χ , emu g
4x10
5
2x10
5
1x10
0
0
50
100
150
200
250
300
Tempearture T, K
Fig. S2. Reciprocal magnetic susceptibility (χ-1) as a function of temperature (T) for
III and IV.
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