Journal of Inorganic and Organometallic Polymers and Materials

Supporting Information

Journal of Inorganic and Organometallic Polymers and Materials

Synthesis, characterization and properties of some main-chain ferrocene-based polymers containing aromatic units

Wael A. Amera, Haojie Yua[*], Li Wanga*, Sergey Vatsadzeb, Rongbai Tonga

a State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

b Department of Chemistry, M.V. Lomonosov Moscow State University, Moscow 119991, Russia

Table A1.Experimental details for the synthesis of the main-chain ferrocene-based metallomesogenic polymers containing aromatic units

Polymer / 1,1’-ferrocene dicarbonyl chloridea / Diolb / Basec / Molar ratio Fc-(COCl)2 : Diol : Base
g / mmol / mol/L / g / mmol / mol/L / mL / mmol
PCPFD / 0.6229 / 2 / 0.476 / 0.9227 / 2.66 / 0.64 / 0.6 / 4 / 1 : 1.33 : 2
PCRFD / 1.7132 / 5.509 / 0.136 / 2.5069 / 6.555 / 0.162 / 0.47 / 5.839 / 1 : 1.19 : 1.06
PQDFD / 0.9488 / 3.05 / 0.2 / 0.4917 / 3.05 / --- / 6.6 / 6.56 / 1 : 1 : 2.15
PSOFD / 1.6128 / 5.186 / 0.2 / 1.1109 / 5.186 / --- / 11.2 / 11.2 / 1 : 1 : 2.15

aThe temperature of the reaction of PCPFD is 0 C for 16 h but the temperature for PCRFD is 70-75 C for 4 h. On the other hand, the temperature of the reaction of PQDFD and PSOFD is 25 C for 4 h.

b The diols for PCPFD, PCRFD, PQDFD and PSOFD are CP, CR, QD and SO, respectively.

c The base for PCPFD is TEA but the base for PCRFD is Py.The base for PQDFD and PSOFD is NaOH.

Table A2. FTIR analysis data of the synthesized main-chain ferrocene-based polymers containing aromatic units

Polymer / Band assignment
PCPFD / PCRFD / PQDFD / PSOFD
3100 / 3110 / 3100 / 3100 / C-H str. of Cp rings
2970 / 2960 / 2960 / 2960 / Aliphatic C-H str.
1730 / 1730 / 1740 / 1740 / C=O str.
1270 / 1270 / 1270 / 1270 / C-O-C str.
1110 / 1100 / 1100 / 1100 / C-O str.
800 / 802 / 820 / 804 / C-H bend.
490 / 486 / 490 / 490 / Cp-Fe str.

Table A3. Electrochemical data of the main-chain ferrocene-based polymers with aromatic units: PCPFD, PCRFD, PQDFD and PSOFD in different organic solvents

Polymer / Solvent / Epc (V) / Epa (V) / Ep1/2 (V) / ΔEp (V) / ipc (μA) / ipa (μA) / ipa/ipc
PCPFD / DMSO / 0.415 / 0.513 / 0.464 / 0.098 / 1.302 / 1.011 / 0.776
DMF / --- / 1.342 / 0.671 / 1.342 / --- / 0.9 / ---
CHCl3 / 1.088 / 1.276 / 1.182 / 0.188 / 1.294 / 0.8713 / 0.673
CH2Cl2 / 1.21 / 1.294 / 1.252 / 0.084 / 2.472 / 1.602 / 0.648
THF / 1.342 / --- / 0.671 / -1.342 / 0.037 / --- / ---
PCRFD / DMSO / 0.34 / 0.489 / 0.4145 / 0.149 / 2.548 / 2.134 / 0.838
DMF / 0.522 / 1.256 / 0.889 / 0.734 / 1.804 / 12.43 / 6.89
CHCl3 / 0.153 / 1.219 / 0.686 / 1.066 / 1.25 / 4.469 / 3.575
CH2Cl2 / 1.133 / 1.241 / 1.187 / 0.108 / 3.275 / 3.199 / 0.977
PQDFD / DMSO / 0.357 / 0.461 / 0.409 / 0.104 / 1.763 / 0.9715 / 0.551
DMF / 0.487 / ----- / 0.2435 / -0.487 / 1.304 / ----- / -----
CHCl3 / 1.054 / 1.286 / 1.17 / 0.232 / 2.304 / 2.371 / 1.029
CH2Cl2 / 1.197 / 1.305 / 1.251 / 0.108 / 5.849 / 3.064 / 0.524
THF / 1.248 / 1.413 / 1.3305 / 0.165 / 1.575 / 3.035 / 1.927
PSOFD / DMSO / 0.282 / 0.461 / 0.3715 / 0.179 / 1.165 / 0.4572 / 0.392
DMF / ----- / 1.049 / 0.5245 / 1.049 / ----- / 3.27 / -----
CHCl3 / 1.121 / 1.266 / 1.1935 / 0.145 / 1.473 / 2.138 / 1.451
CH2Cl2 / 1.213 / 1.282 / 1.2475 / 0.069 / 1.94 / 5.442 / 2.805
THF / 1.259 / 1.389 / 1.324 / 0.13 / 1.816 / 1.053 / 0.580

Table A4.Electrochemical data of the main-chain ferrocene-based polymers with aromatic units: PCPFD, PCRFD, PQDFD and PSOFD at different scan rates

Polymer / Scan rate (V/s) / Epc (V) / Epa (V) / Ep1/2 (V) / ΔEp (V) / ipc (μA) / ipa (μA) / ipa/ipc
PCPFD / 0.1 / 0.415 / 0.513 / 0.464 / 0.098 / 1.302 / 1.011 / 0.776
0.2 / 0.425 / 0.521 / 0.473 / 0.096 / 2.189 / 1.751 / 0.8
0.3 / 0.431 / 0.532 / 0.482 / 0.101 / 2.627 / 1.807 / 0.688
0.4 / 0.435 / 0.544 / 0.49 / 0.109 / 3.335 / 2.259 / 0.677
0.5 / 0.433 / 0.551 / 0.492 / 0.118 / 3.964 / 2.664 / 0.672
PCRFD / 0.1 / 1.133 / 1.241 / 1.187 / 0.108 / 3.275 / 3.199 / 0.977
0.2 / 1.116 / 1.238 / 1.177 / 0.122 / 5.916 / 10.71 / 1.81
0.3 / 1.101 / 1.225 / 1.163 / 0.124 / 8.129 / 12.16 / 1.496
0.4 / 1.072 / 1.211 / 1.1415 / 0.139 / 10.55 / 13.79 / 1.307
0.5 / 1.049 / 1.208 / 1.1285 / 0.159 / 12.75 / 15.56 / 1.22
PQDFD / 0.1 / 0.357 / 0.461 / 0.409 / 0.104 / 1.763 / 0.9715 / 0.551
0.2 / 0.383 / 0.481 / 0.432 / 0.098 / 3.211 / 1.865 / 0.581
0.3 / 0.391 / 0.487 / 0.439 / 0.096 / 4.389 / 2.686 / 0.612
0.4 / 0.394 / 0.492 / 0.443 / 0.098 / 5.23 / 3.179 / 0.608
0.5 / 0.397 / 0.498 / 0.4475 / 0.101 / 6.64 / 4.244 / 0.639
PSOFD / 0.1 / 0.282 / 0.461 / 0.3715 / 0.179 / 1.165 / 0.4572 / 0.392
0.2 / 0.312 / 0.486 / 0.399 / 0.174 / 2.205 / 0.9968 / 0.452
0.3 / 0.324 / 0.489 / 0.4065 / 0.165 / 3.106 / 1.249 / 0.402
0.4 / 0.327 / 0.501 / 0.414 / 0.174 / 3.957 / 1.62 / 0.409
0.5 / 0.336 / 0.509 / 0.4225 / 0.173 / 4.289 / 1.888 / 0.440

Table A5.Relationships among the peak currents, the peak potentials, and scan rates for PCPFD, PCRFD, PQDFD and PSOFD

Polymer / Rate range (V/s) / Linear equation / Correlation coefficient
PCPFD / 0.1-0.5
0.1-0.5
0.2-0.5
0.2-0.5 / ipc (µA) = -0.836 + 6.638 υ1/2
ipa (µA) = -0.188 + 3.936 υ1/2
ln ipc (µA) = -15.583 – 53.789 (Epc-Ep1/2)
ln ipa (µA) = -15.23 + 40.594 (Epc-Ep1/2) / 0.99
0.94
0.97
0.96
PCRFD / 0.1-0.5
0.1-0.5
0.1-0.5
0.2-0.5 / ipc (µA) = -4.677 + 24.146 υ1/2
ipa (µA) = -4.617 + 29.617 υ1/2
ln ipc (µA) = -15.128 – 50.689 (Epc-Ep1/2)
ln ipa (µA) = -12.468 + 17.826 (Epc-Ep1/2) / 0.99
0.89
0.79
0.85
PQDFD / 0.1-0.5
0.1-0.5
0.1-0.3
0.3-0.5
0.1-0.3
0.3-0.5 / ipc (µA) = -2.155 + 12.075 υ1/2
ipa (µA) = -1.670 + 8.033 υ1/2
ln ipc (µA) = -1.742 + 221.521 (Epc-Ep1/2)
ln ipc (µA) = -20.257 – 165.093 (Epc-Ep1/2)
ln ipa (µA) = -1.083 – 245.738 (Epa-Ep1/2)
ln ipa (µA) = -21.653 + 183.743 (Epa-Ep1/2) / 0.99
0.97
0.98
0.99
0.97
0.99
PSOFD / 0.1-0.5
0.1-0.5
0.1-0.5a
0.1-0.5a / ipc (µA) = -1.456 + 8.301 υ1/2
ipa (µA) = -0.668 + 3.603 υ1/2
ln ipc (µA) = 22.665 + 406.131 (Epc-Ep1/2)
ln ipa (µA) = 25.092 – 443.709 (Epa-Ep1/2) / 0.99
0.99
0.74
0.83

aThe point at 0.3 V/s was not considered in the relationship.

Table A6.Electrochemical data of the main-chain ferrocene-based polymers with aromatic units: PCPFD, PCRFD, PQDFD and PSOFD at different electrolyte concentrations

Polymer / Electrolyte concentration (mol/L) / Epc (V) / Epa (V) / Ep1/2 (V) / ΔEp (V) / ipc(μA) / ipa(μA) / ipa/ipc
PCPFD / 0.01 / 0.363 / 0.546 / 0.455 / 0.183 / 1.395 / 0.816 / 0.585
0.025 / 0.337 / 0.498 / 0.418 / 0.161 / 1.48 / 0.814 / 0.55
0.05 / 0.357 / 0.502 / 0.43 / 0.145 / 1.507 / 0.886 / 0.588
0.075 / 0.42 / 0.501 / 0.461 / 0.081 / 1.237 / 0.924 / 0.747
0.1 / 0.415 / 0.513 / 0.464 / 0.098 / 1.302 / 1.011 / 0.776
PCRFD / 0.01 / 0.891 / 1.324 / 1.1075 / 0.433 / 7.869 / 6.82 / 0.867
0.025 / 1.013 / 1.242 / 1.1275 / 0.229 / 9.452 / 9.71 / 1.027
0.05 / 1.067 / 1.226 / 1.1465 / 0.159 / 7.095 / 4.879 / 0.688
0.075 / 1.099 / 1.219 / 1.159 / 0.12 / 6.24 / 4.936 / 0.791
0.1 / 1.133 / 1.241 / 1.187 / 0.108 / 3.275 / 3.199 / 0.977
PQDFD / 0.01 / 0.235 / 0.454 / 0.3445 / 0.219 / 1.926 / 0.6716 / 0.349
0.025 / 0.231 / 0.419 / 0.325 / 0.188 / 1.984 / 0.7628 / 0.384
0.05 / 0.307 / 0.461 / 0.384 / 0.154 / 1.658 / 0.8919 / 0.538
0.075 / 0.356 / 0.467 / 0.4115 / 0.111 / 1.641 / 0.8895 / 0.542
0.1 / 0.357 / 0.461 / 0.409 / 0.104 / 1.763 / 0.9715 / 0.551
PSOFD / 0.01 / 0.215 / 0.432 / 0.3235 / 0.217 / 1.248 / 0.0088 / 0.007
0.025 / 0.255 / 0.454 / 0.3545 / 0.199 / 1.512 / 0.4387 / 0.290
0.05 / 0.288 / 0.482 / 0.385 / 0.194 / 1.575 / 0.6158 / 0.391
0.075 / 0.306 / 0.483 / 0.3945 / 0.177 / 1.49 / 0.5372 / 0.361
0.1 / 0.282 / 0.461 / 0.3715 / 0.179 / 1.165 / 0.4572 / 0.392

Table A7.Relationships among the peak currents, the peak potentials and the scan rates for PCPFD at different concentrations of the electrolyte

Electrolyte concentration (mol/L) / Scan Rate range (V/s) / Linear equation / Correlation coefficient
0.01 / 0.1 – 0.5 / ipc (µA) = -0.102 + 4.901 1/2
ipa (µA) = 0.056 + 2.81 1/2
ln ipc (µA) = -16.562 – 34.459 (Epc – Ep1/2)
ln ipa (µA) = -16.933 + 33.421 (Epa – Ep1/2) / 0.99
0.9
0.95
0.82
0.025 / 0.1 – 0.5 / ipc (µA) = -0.96 + 7.542 1/2
ipa (µA) = -1.027 + 5.76 1/2
ln ipc (µA) = -17.431 – 52.322 (Epc – Ep1/2)
ln ipa (µA) = -18.741 + 62.191 (Epa – Ep1/2) / 0.99
0.99
0.78
0.76
0.05 / 0.1 – 0.5
0.1 – 0.5
0.2 – 0.5
0.2 – 0.5 / ipc (µA) = -0.85 + 7.433 1/2
ipa (µA) = -0.552 + 5.193 1/2
ln ipc (µA) = -15.33 – 52.917 (Epc – Ep1/2)
ln ipa (µA) = -14.856 + 37.805 (Epa – Ep1/2) / 0.95
0.9
0.9
0.96
0.075 / 0.1 – 0.5 / ipc (µA) = -1.58 + 8.915 1/2
ipa (µA) = -1.22 + 6.541 1/2
ln ipc (µA) = -16.433 – 79.316 (Epc – Ep1/2)
ln ipa (µA) = -16.971 + 83.612 (Epa – Ep1/2) / 0.99
0.97
0.64
0.74
0.1 / 0.1 – 0.5
0.1 – 0.5
0.2 – 0.5
0.2 – 0.5 / ipc (µA) = -0.836 + 6.638 υ1/2
ipa (µA) = -0.188 + 3.936 υ1/2
ln ipc (µA) = -15.583 – 53.789 (Epc-Ep1/2)
ln ipa (µA) = -15.23 + 40.594 (Epc-Ep1/2) / 0.99
0.94
0.97
0.96

Table A8.Relationships among the peak currents, the peak potentials and the scan rates for PCRFD at different concentrations of the electrolyte

Electrolyte concentration (mol/L) / Scan Rate range (V/s) / Linear equation / Correlation coefficient
0.01 / 0.2 – 0.4 / ipa (µA) = 8.305 – 3.192 1/2 a
ln ipa (µA) = -11.862 – 0.18 (Epa – Ep1/2) a / 0.76
0.97
0.025 / 0.1 – 0.4 / ipc (µA) = 0.697 + 28.623 1/2
ipa (µA) = 2.433 + 23.316 1/2
ln ipc (µA) = -12.194 – 6.02 (Epc – Ep1/2)
ln ipa (µA) = -12.087 + 5.096 (Epa – Ep1/2) / 0.98
0.99
0.9
0.94
0.05 / 0.1 – 0.5 / ipc (µA) = -13.767 + 68.321 1/2
ipa (µA) = -15.667 + 69.545 1/2
ln ipc (µA) = -12.72 – 14.425 (Epc – Ep1/2)
ln ipa (µA) = -13.161 + 16.991 (Epa – Ep1/2) / 0.99
0.98
0.82
0.74
0.075 / 0.1 – 0.5 / ipc (µA) = -15.414 + 61.753 1/2 a
ipa (µA) = -18.479 + 65.291 1/2 a
ln ipc (µA) = -13.735 – 27.935 (Epc – Ep1/2)
ln ipa (µA) = -14.372 + 33.13 (Epa – Ep1/2) / 0.94
0.9
0.94
0.9
0.1 / 0.1 – 0.5
0.1 – 0.5
0.1 – 0.5
0.2 – 0.5 / ipc (µA) = -4.677 + 24.146 υ1/2
ipa (µA) = -4.617 + 29.617 υ1/2
ln ipc (µA) = -15.128 – 50.689 (Epc-Ep1/2)
ln ipa (µA) = -12.468 + 17.826 (Epc-Ep1/2) / 0.99
0.89
0.79
0.85

a The point 0.3 V/s was not considered in the linear relationship.

Table A9.Relationships among the peak currents, the peak potentials and the scan rates for PQDFD at different concentrations of the electrolyte

Electrolyte concentration (mol/L) / Scan Rate range (V/s) / Linear equation / Correlation coefficient
0.01 / 0.1-0.5
0.1-0.5
0.1-0.5
0.2-0.5 / ipc (µA) = -1.381 + 10.394 1/2
ipa (µA) = 0.053 – 2.444 1/2
ln ipc (µA) = -16.082 – 28.416 (Epa – Ep1/2)
ln ipa (µA) = -14.939 – 20.089 (Epa – Ep1/2) / 0.99
0.8
0.86
0.95
0.025 / 0.1-0.5
0.1-0.5
0.3-0.5
0.3-0.5 / ipc (µA) = -1.700 + 11.624 1/2
ipa (µA) = -0.528 + 4.556 1/2
ln ipc (µA) = -14.053 – 19.154 (Epc – Ep1/2)
ln ipa (µA) = -14.527 + 15.164 (Epa – Ep1/2) / 0.99
0.95
0.94
0.97
0.05 / 0.1-0.5
0.1-0.5
0.2-0.5
0.2-0.5 / ipc (µA) = -2.090 + 11.712 1/2
ipa (µA) = -0.688 + 4.976 1/2
ln ipc (µA) = -13.715 – 18.670 (Epc – Ep1/2)
ln ipa (µA) = -14.324 + 16.781 (Epa – Ep1/2) / 0.99
0.99
0.94
0.97
0.075 / 0.1 – 0.5 / ipc (µA) = -2.229 + 12.004 1/2
ipa (µA) = -0.741 + 5.034 1/2
ln ipc (µA) = -18.563 – 94.623 (Epc – Ep1/2)
ln ipa (µA) = -18.467 + 81.592 (Epa – Ep1/2) / 0.99
0.99
0.95
0.93
0.1 / 0.1-0.5
0.1-0.5
0.1-0.3
0.3-0.5
0.1-0.3
0.3-0.5 / ipc (µA) = -2.155 + 12.075 υ1/2
ipa (µA) = -1.670 + 8.033 υ1/2
ln ipc (µA) = -1.742 + 221.521 (Epc – Ep1/2)
ln ipc (µA) = -20.257 – 165.093 (Epc – Ep1/2)
lnipa (µA) = -1.083 – 245.738 (Epa – Ep1/2)
ln ipa (µA) = -21.653 + 183.743 (Epa – Ep1/2) / 0.99
0.97
0.98
0.99
0.97
0.99

Table A10. Relationships among the peak currents, the peak potentials and the scan rates for PSOFD at different concentrations of the electrolyte

Electrolyte concentration (mol/L) / Scan Rate range (V/s) / Linear equation / Correlation coefficient
0.01 / 0.1 – 0.5
0.2 – 0.4
0.2 – 0.4
0.2 – 0.4 / ipc (µA) = -1.256 + 8.269 1/2
ipa (µA) = 0.873 – 1.689 1/2
ln ipc (µA) = -14.661 – 17.311 (Epa – Ep1/2)
ln ipa (µA) = 15.424 – 279.350 (Epa – Ep1/2) / 0.99
0.87
0.83
0.81
0.025 / 0.1 – 0.5
0.1 – 0.5
0.2 – 0.5
0.2 – 0.5 / ipc (µA) = -1.863 + 10.553 1/2
ipa (µA) = -0.177 + 1.927 1/2
ln ipc (µA) = -16.003 – 34.971 (Epc – Ep1/2)
ln ipa (µA) = -16.673 + 26.920 (Epa – Ep1/2) / 0.99
0.97
0.79
0.61
0.05 / 0.1 – 0.5 / ipc (µA) = -2.207 + 11.650 1/2
ipa (µA) = -0.379 + 3.048 1/2
ln ipc (µA) = 13.014 + 270.210 (Epc – Ep1/2) a
ln ipa (µA) = 6.160 – 209.558 (Epa – Ep1/2)a / 0.99
0.99
0.76
0.73
0.075 / 0.1 – 0.5
0.1 – 0.5
0.3 – 0.5
0.3 – 0.5 / ipc (µA) = -2.16 + 11.559 1/2
ipa (µA) = -0.591 + 3.462 1/2
ln ipc (µA) = -25.307 – 145.957 (Epc – Ep1/2)
ln ipa (µA) = -26.960 + 151.358 (Epa – Ep1/2) / 0.99
0.99
0.99
0.99
0.1 / 0.1 – 0.5 / ipc (µA) = -1.456 + 8.301 1/2
ipa (µA) = -0.668 + 3.603 1/2
ln ipc (µA) = 22.665 + 406.131 (Epc – Ep1/2)b
ln ipa (µA) = 25.092 – 443.709 (Epc – Ep1/2)b / 0.99
0.99
0.74
0.83

a The point 0.2 V/s was not considered in the linear relationship.

b The point 0.3 V/s was not considered in the linear relationship.

Table A11.Electrochemical data of the main-chain ferrocene-based polymers with aromatic backbones: PCPFD, PCRFD,PQDFD and PSOFD at different [Fe] concentrations

Polymer / [Fe] mM / Epc (V) / Epa (V) / Ep1/2 (V) / ΔEp (V) / ipc (μA) / ipa (μA) / ipa/ipc
PCPFD / 0.25 / 0.428 / 0.513 / 0.471 / 0.085 / 0.816 / 0.479 / 0.588
0.5 / 0.415 / 0.513 / 0.464 / 0.098 / 1.302 / 1.011 / 0.776
0.75 / 0.443 / 0.527 / 0.485 / 0.084 / 1.455 / 1.153 / 0.792
1 / 0.442 / 0.533 / 0.488 / 0.091 / 1.801 / 1.378 / 0.765
PCRFD / 0.25 / 1.125 / 1.221 / 1.173 / 0.096 / 3.562 / 3.449 / 0.968
0.5 / 1.133 / 1.241 / 1.187 / 0.108 / 3.275 / 3.199 / 0.977
0.75 / 1.083 / 1.202 / 1.1425 / 0.119 / 9.784 / 5.63 / 0.575
1 / 1.069 / 1.203 / 1.136 / 0.134 / 14.06 / 9.307 / 0.662
PQDFD / 0.25 / 0.358 / 0.467 / 0.4125 / 0.109 / 1.487 / 0.8239 / 0.554
0.5 / 0.357 / 0.461 / 0.409 / 0.104 / 1.763 / 0.9715 / 0.551
0.75 / 0.358 / 0.473 / 0.4155 / 0.115 / 2.482 / 1.437 / 0.579
1 / 0.358 / 0.486 / 0.422 / 0.128 / 2.899 / 1.766 / 0.609
PSOFD / 0.25 / 0.306 / 0.472 / 0.389 / 0.166 / 1.188 / 0.2672 / 0.225
0.5 / 0.282 / 0.461 / 0.3715 / 0.179 / 1.165 / 0.4572 / 0.392
0.75 / 0.273 / 0.462 / 0.3675 / 0.189 / 1.808 / 0.8087 / 0.447
1 / 0.279 / 0.486 / 0.3825 / 0.207 / 2.128 / 1.003 / 0.471

Table A12.Thermal properties of the synthesized main-chain ferrocene-based polymers with aromatic backbones

Polymer / T5 (C) / T10 (C) / Ts (C) / Char yield at 800 C (%)
PCPFD / 183.4 / 315.7 / 399.7 / 29.2 a
PCRFD / 208.4 / 236.6 / 395.7 / 22.7
PQDFD / 333.8 / 400.4 / 676.3 / 60.3
PSOFD / 272.6 / 316 / 736 / 43.6

a The char yield of PCPFD was determined at 780.6 C.

Figure A1. DSC curves of the second heating cycle of the aromatic main-chain ferrocene-based polymers PCPFD, PCRFD, PQDFD and PSOFD.

[*]Correspondence to: Haojie Yu and Li Wang (Tel: +86-571-8795-3200, Fax: +86-571-8795-1612, E-mail: and )