# Fileset

[macp202400506-sup-0001-suppmat.docx](https://mdr.nims.go.jp/filesets/069c71ce-9628-425e-90b8-c6578ed9595b/download)

## Creator

Ziwei Hu, [Takeshi Yasuda](https://orcid.org/0000-0003-4652-9105), Takaki Kanbara, [Junpei Kuwabara](https://orcid.org/0000-0002-9032-5655)

## Rights

[Creative Commons BY-NC-ND Attribution-NonCommercial-NoDerivs 4.0 International](https://creativecommons.org/licenses/by-nc-nd/4.0/)

## Other metadata

[Synthesis of Conjugated Polymers with Controlled Terminal Structures by Direct Arylation Polycondensation and Correlation Between Terminal Structures and Emission Properties](https://mdr.nims.go.jp/datasets/22835d68-9b9d-40e1-a412-a4e02f013538)

## Fulltext

Supporting InformationSynthesis of Conjugated Polymers with Controlled Terminal Structures by Direct Arylation Polycondensation and Correlation between Terminal Structures and Emission PropertiesZiwei Hu,a Takeshi Yasuda,b Takaki Kanbara, a* Junpei Kuwabara a,c*Scheme S1. Synthesis of the Pd(II) catalyst precursor.Scheme S2. Polycondensation and terminal modification by the Pd(II) catalyst precursor.Table S1. Results of polycondensation Entry TPD : Br2-DOF Yield a) Mn (Mw/Mn) Theoretical Mn b) 1 1 : 1.05 73% 120 000 (2.6) 24 600 2 1 : 1.33 77% 16 900 (1.8) 4 900a) Yields of the CHCl3-soluble and hexane-insoluble parts. b) Calculated by the Carothers equation.Figure S1. MALDI-TOF-MS of the polymer (Table 1, Entry 1).Figure S2. MALDI-TOF-MS of the polymer (Table 1, Entry 2).Figure S3. MALDI-TOF-MS of the polymer (Table 1, Entry 3).Figure S4. 1H NMR Spectrum of the terminal modified polymer (600 MHz, CDCl3, r.t.).Figure S5. MALDI-TOF-MS tracking the terminal modification process using Pd(PCy3)2.Figure S6. 1H NMR spectrum of the Pd(II) catalyst precursor. (400 MHz, CDCl3).Figure S7. 13C{1H} NMR spectrum of the Pd(II) catalyst precursor (100 MHz, CDCl3).Figure S8. 31P NMR spectrum of the Pd(II) catalyst precursor (162 MHz, CDCl3).Figure S9. 1H NMR spectrum of P-Th (600 MHz, C2D2Cl4, 373 K).Figure S10. 1H NMR spectrum of P-TPD (600 MHz, C2D2Cl4, 373 K).Figure S11. 1H NMR spectrum of P-Br (600 MHz, C2D2Cl4, 373 K).Figure S12. UV-Vis absorption spectra (a) in the solution (CHCl3, 5 μM) and (b) thin-film states.Figure S13. Voltage (V) – Luminance (L) characteristics of the OLEDs.Figure S14. Normalized EL spectrum of the OLED with P-TPD and PL spectrum in thin-film state.9image1.emfPd2(dba)3    +   PCy3    +SBrtoluene60 ℃, 24 hPCy3 =P3(4 equiv.)(2 equiv.)PdPCy3PCy3BrSimage2.emf+SNOOEHHHOct OctBrBr1.01              :                1Cs2CO3,PivOHtoluene100 ℃, 24 hPdPCy3PCy3BrS(2 mol%)Oct OctSNOOHEHSNO OEHn100 ℃, 24 hPdPCy3PCy3BrS(2 mol%)Oct OctSNO OEHSNO OEHSSnBrSYield 93%, Mn= 31 000, Mw/Mn= 1.7Simage3.emf+SNOOEHHHEH = 2-EthylhexylOct OctSNO OEHPd(PCy3)2 (2 mol%)PivOH (30 mol%)Cs2CO3(2.5 equiv.)Oct OctBr Brnn ntoluene100 ℃, 24 himage4.emf01020304050607080901003300 4300 5300 6300 7300 8300 9300% IndensityMass (m/Z)Peak 1Peak 1OctOctSNO OHEHSNO OEH5HMass / m/zRepeating unit% Intensityimage5.pngimage6.pngimage7.pngimage8.emfOctOctSNO OHEHSNO OEHHnOctOctSNO OEHSNO OEHSS nBrSPd(PCy3)2  (2 mol%)PivOH , Cs2CO3  toluene100 ℃, 24 himage9.emf02040608010001020304050607080901004000 4500 5000 5500 6000 6500010203040506070010203040506070010203040506070010203040506070ABCa 0hb 2hc 4hd 6he 8hf 24hMass / m/zimage10.emfOct OctSNO OHEHSNO OEHHOct OctSNO OEHSNO OEHSSA COct OctSNOOHEHSNOOEHSBnn nimage11.jpegimage12.jpegimage13.jpegimage14.jpgimage15.jpgimage16.jpegimage17.emf00.20.40.60.811.2300 350 400 450 500 550 600Absorbance / a.u.Wavelength / nmP-ThP-HP-Br(a)00.20.40.60.811.2300 350 400 450 500 550 600Absorbance / a.u.Wavelength / nmP-ThP-HP-Br(b)P-TPD P-TPD00.20.40.60.811.2300 350 400 450 500 550 600Absorbance / a.u.Wavelength / nmP-ThP-HP-Br(a)00.20.40.60.811.2300 350 400 450 500 550 600Absorbance / a.u.Wavelength / nmP-ThP-HP-Br(b)P-TPDP-TPDimage18.emf0.0010.010.11101001000100001000000 2 4 6 8 10 12 14 1610610510410310210110010-110-210-3Luminance / cd m -20 5 10 15Voltage / V00.20.40.60.811.21.40.001 0.01 0.1 1 10 100 1000P-ThP-HP-BrP-TPD0 . 0 010 . 010 .11101 001 0 001 0 0 001 0 0 0 000 2 4 6 8 10 12 14 1610610510410310210110010-110-210-3Luminance / cd m -20 5 10 15Voltage / V00 . 20 . 40 . 60 . 811 . 21 . 40 . 0 0 1 0.01 0 . 1 1 1 0 1 0 0 1 0 0 0P-ThP-HP-BrP-TPDimage19.emf00.20.40.60.811.2450 500 550 600 650 700 750 800EL and PL intensity / a.u.Wavelength / nmP-TPD-ELP-TPD-PL00.20.40.60.811.2450 500 550 600 650 700 750 800EL and PL intensity / a.u.Wavelength / nmP-TPD-ELP-TPD-PLimage20.jpeg