Ecz400 spectrometer

Compounds were analyzed using Varian 400 MHz and 600 MHz systems (now Agilent) at the Okayama University Collaboration Center, and also using a JEOL ECZ400 spectrometer at the Kobe University Department of Chemical Science and Engineering. Measurements were taken with 2-4 dissolved in CDCl₃, and 5-8 dissolved in CD₃OD. NMR chemical shifts (δ) are provided in parts per million (ppm).¹H-NMR coupling constants (J) are listed in Hz. Residual peaks of chloroform (7.26 ppm) and methanol (3.31 ppm) were used as¹H-NMR references. The residual peaks of chloroform (77.0 ppm) and methanol (49.0 ppm) were also used as¹³C-NMR references. For 2D experiments, the standard pulse sequences programmed into the Varian NMR systems were used. 2D-NOESY experiments were performed at room temperature with a spectral width of 9615.4 Hz (sw), an acquisition time of 0.15 seconds (at), 2844 data points (np), a filter bandwidth of 4000 Hz (fb), a relaxation delay of 2.000 seconds (d1), 4 transients (nt), 128 or 200 experiments (ni), a pulse width of 9.700 or 10.900 microseconds (pw) and a mixing time 0.500 seconds (mixN).

1D and 2D NMR spectra were recorded on an ECZ-400 spectrometer (Jeol Ltd., Tokyo, Japan). The signals of the solution CDCl₃ (residual CHCl₃ (δ_H 7.26 ppm) and CDCl₃ (δ_C 77.0 ppm)) were used as internal standards. NMR data were acquired and processed with Delta 6.1.0 or MestReNova v12.2.2 software. MS and HRMS spectra were acquired on an SolariX FTMS mass spectrometer (7 Tesla; Bruker, Bremen, Germany) with an ESI ion source in positive ionization mode. Silica gel (Kieselgel 60, 70–230 or 230–400 mesh, Merck, Darmstadt, Germany), and Sephadex LH-20 gel (Pharmacia Fine Chemicals AB, Uppsala, Sweden) were used for column chromatography (CC). Thin-layer chromatography (TLC) was carried out using silica gel (Kieselgel 60 F₂₅₄, Merck) and RP-C18 (F_254s, Merck) pre-coated plates. For visualization, the compounds were detected on TLC with a developer (50% H₂SO₄ (v/v) in methanol) followed by heating at 120 °C. HPLC analyses were performed with a pump (model L-2130, Hitachi, Tokyo, Japan) and a diode-array detector (model L-2455, Hitachi, Tokyo, Japan) equipped with an HPLC analytical column (BDS Hypersil^TM C18, 250 × 4.6 mm, 5 μm, ThermoFisher Scientific Inc., Waltham, MA, USA), and using a mixture of acetonitrile (ACN)/H₂O or a mixture of methanol (MeOH)/H₂O as the mobile phase (Supplementary Fig. 13).

UV-Vis-NIR spectra were measured using a V-670 spectrophotometer (JASCO, Tokyo, Japan) and the ¹H-NMR spectra were recorded using a JEOL ECZ-400 spectrometer (Tokyo, Japan). The TGA spectrum was measured using a differential scanning calorimeter DSC6000 (HITACHI, Tokyo, Japan). Before measuring TGA, the polymers were dried under vacuum overnight.
The reduced viscosity (η_sp/C) was measured using an Ubbelohde-type viscometer with a 4.0 g/L sample solution at 30 °C. The molecular weights of the polymers were roughly estimated using the Equation (1)

where, k (1.16 × 10⁻⁵) and α (0.894) were approximated from the η_sp/C and M_w values determined via ultracentrifugal analysis.
To prepare the pressed samples (Figure 1), the polymer (0.010 g) was filled into ClearDisc CD-10 and pressurized to 10 kN using a hydraulic press. The electric resistance of samples was determined using a four-probe resistivity measurement device (MCP-T410, Mitsubishi Chemical Holdings, Tokyo, Japan). The conductivity was calculated by Equations (2) and (3)


where, ρ_V: volume resistivity (Ωcm), R: resistance (Ω), RCF: resistivity correction factor, t: thickness (cm), σ: conductivity (S/cm)
Band gap was estimated from the absorption edge using the Equation (4)

where, α, v, and E_g are the absorption coefficient, light frequency, and band gap energy, respectively.