Electronic Supplementary Material (ESI) for Polymer Chemistry. This journal is © The Royal Society of Chemistry 2014 Supplementary Information for The Pd(AcO)2/t-Bu3P/K3PO4 catalytic system for the control of the Suzuki cross-coupling polymerisation by Roberto Grisorio, Piero Mastrorilli and Gian Paolo Suranna DICATECh - Dipartimento di Ingegneria Civile, Ambientale, del Territorio, Edile e di Chimica del Politecnico di Bari, via Orabona, 4 I-70125 Bari, Italy 1 Figure S1. 1H-NMR spectrum of 2,7-diphenyl-9,9-di-n-octylfluorene. 2 Figure S2. 13C{1H}-NMR spectrum of 2,7-diphenyl-9,9-di-n-octylfluorene. 3 4000 Intensity (a.u.) 3000 2000 1000 0 360 370 380 390 400 410 420 m/z Figure S3. HRMS(+) spectrogram of the reaction mixture obtained according to Method A (1 equiv t-Bu3P) showing complex  as Na-adduct. 12000 Intensity (a.u.) 10000 8000 6000 4000 2000 0 490 495 500 505 510 515 520 525 530 m/z Figure S4. HRMS(+) spectrogram of the reaction mixture obtained according to Method A (2 equiv t-Bu3P) showing complex  as [M – AcO]+. 4 Figure S5. Typical 1H-NMR spectrum of the poly(9,9-di-n-octylfluorene)s obtained by method B. 5 Figure S6. HRMS(+) spectrogram of the products obtained according to Method B with a FL/Pd(AcO)2 molar ratio of 2/1. 6 Figure S7. 1H-NMR spectrum (aromatic region) of the polymer isolated from entry 12. 7 Figure S8. 1H-NMR spectrum (aromatic region) of the polymer isolated from entry 13. Figure S9. 1H-NMR spectrum (aromatic region) of the polymer isolated from entry 14. 8 entry 12 (27000 Da) entry 13 (17900 Da) entry 14 (10000 Da) 5,0 5,5 6,0 6,5 7,0 7,5 8,0 8,5 9,0 Elution time (min) Figure S10. GPC traces of the isolated polymers (Table 1 of the manuscript, entries 12-14). 35000 30000 Mn (Da) 25000 20000 15000 10000 5000 0 5 10 15 20 25 Monomer/Pd(AcO)2 Figure S11. Number-average molecular weights (Mn) vs monomer/Pd(AcO)2 feed ratio of the isolated polymers (Table 1 of the manuscript, entries 12-14). 9