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1 Efficient Greenish Blue Electrochemiluminescence from Fluorene and Spirobifluorene Derivatives Federico Polo, *,, Fabio Rizzo, *, Manoel Veiga Gutierrez, Luisa De Cola, Silvio Quici Physikalisches Institut, Westfälische Wilhelms-Universität, Heisenbergstrasse 11, D Münster, Germany; Istituto di Scienze e Tecnologie Molecolari (ISTM) CR, Via Golgi 19, I Milano, Italy; Polo Scientifico Tecnologico (PST) CR, Via Fantoli 16/15, I Milano, Italy. Current Address: Dipartimento di Scienze Chimiche, Università degli Studi di Padova, Via Marzolo 1, I Padova, Italy Supporting Information S1

2 General Experiments. All solvents and reagents used are commercially available and were employed as received without further purifications. TLC was carried out on silica gel Si 60-F254. Column chromatography was carried out on silica gel Si 60, mesh size mm (Merck, Darmstadt, Germany). Flash chromatography was carried out on J. T. Baker silica gel mesh size H MR (400 MHz) and 13 C MR (101 MHz) spectra were recorded in CDCl 3 with a Bruker Avance 400 spectrometer. The assignment of protons and carbon atoms was carried out by bidimensional MR experiments (COSY, heterocorrelate 1 H- 13 C). The coupling constants J are given in Hz. Mass analyses were performed by Fourier Transform Ion Cyclotron Resonance (FT-ICR) Mass Spectrometer APEX II and Xmass Software (Bruker Daltonics) at the Centro Interdipartimentale Grandi Apparecchiature (Università di Milano). Melting points (uncorrected) were determined with a Buchi Melting Point B- 540 capillary melting point apparatus. Compounds 2,2 -dibromo-9,9 -dimethyl-fluorene (4), 1 2,2 - dibromo-9,9 -spirobifluorene (5), 2 2,2,7,7 -tetrabromo-9,9 -spirobifluorene (6) 3 were synthesized according to the respective literature procedures. All coupling reactions are been performed under nitrogen using Schlenk technique. 2,7-bis-(4-(,-diphenylamino)phen-1-yl)-9,9 -dimethyl-fluorene (1). In a Schlenk tube a stirred mixture of 2,7-dibromo-9,9 -dimethyl-fluorene (4) (204.8 mg, mmol), 4-(,diphenylamino)phenylboronic acid (310.2 mg, mmol), aqueous a 2 CO 3 2M (3 ml), Pd(PPh 3 ) 4 (65.1 mg, mmol) in dry THF (8 ml) was refluxed overnight under inert atmosphere. After cooling at room temperature, the organic solvent was removed under vacuum and the solid dissolved in CH 2 Cl 2. The aqueous phase was extracted with CH 2 Cl 2 (2 x 10 ml) and the collected organic phases were washed with water (1 x 30 ml), and dried over a 2 SO 4. After removing the solvent under vacuum, the product was purified by column chromatography over silica using the mixture hexane/ch 2 Cl 2 (4:1) as eluent to give the product as white solid (234.3 mg, 60 %). 1 H MR (400 MHz, CDCl 3, 25 C): δ = 7.77 (d, J H-H = 7.89 Hz, 2 H, 4-H, 5-H), 7.64 (d, J H-H = 1.42 Hz, 2 H, 1-H, 8-H), (m, 6 H, 3- H, 6-H, 2-H phenyl, 6-H phenyl), (m, 8 H, H phenyl), (m, 12 H, 3-H phenyl, 5- H phenyl, H phenyl), 7.05 (t br, J H-H = 7.30 Hz, 4 H, H phenyl), 1.58 (s, 6 H, CH 3 ) ppm. 13 C MR (101 MHz, CDCl 3, 25 C): δ = (q), (q), (q), (q), (q), (q), S2

3 (phenyl), (2-C phenyl, 6-C phenyl), (3-C, 6-C), (phenyl), (phenyl), (phenyl), (1-C, 8-C), (4-C, 5-C), (9-C), (CH 3 ) ppm. M.p.: C. m/z (HRMS ESI + ): (M +. C 51 H 40 2 requires ), (M 2+. C 51 H 40 2 requires ). UV/Vis (CHCl 3 ): λ max (ε) = 369 (65370), 305 nm (31130 mol -1 dm 3 cm -1 ). 2,7-bis-(4-(,-diphenylamino)phen-1-yl)-9,9 -spirobifluorene (2). In a Schlenk tube a stirred mixture of 2,7-dibromo-9,9 -spirobifluorene (5) (230.1 mg, mmol), 4-(,diphenylamino)phenylboronic acid (310.2 mg, mmol), aqueous a 2 CO 3 2M (3 ml), Pd(PPh 3 ) 4 (65.1 mg, mmol) in dry THF (8 ml) was refluxed overnight under inert atmosphere. After cooling at room temperature, the organic solvent was removed under vacuum and the solid dissolved in CH 2 Cl 2. The aqueous phase was extracted with CH 2 Cl 2 (2 x 10 ml) and the collected organic phases were washed with water (1 x 30 ml), and dried over a 2 SO 4. After removing the solvent under vacuum, the product was purified by column chromatography over silica using the mixture hexane/ch 2 Cl 2 (4:1) as eluent to give the product as white solid (234.3 mg, 60 %). 1 H MR (400 MHz, CDCl 3, 25 C): δ = 7.89 (d, J H-H = 7.96 Hz, 2 H, 4-H, 5-H), 7.86 (d, J H-H = 7.62 Hz, 2 H, 4 -H, 5 -H), 7.60 (dd, J H-H = 7.96 Hz, J H-H = 1.68 Hz, 2 H, 3-H, 6-H), 7.37 (dt, J H-H = 7.51 Hz, J H-H = 0.84 Hz, 2 H, 3 -H, 6 -H), 7.30 (d, J H-H = 8.66 Hz, 4 H, 2-H aminophenyl, 6-H aminophenyl), (m, 8 H, H phenyl), 7.12 (dt, J H- H = 7.56 Hz, J H-H = 1.00 Hz, 2 H, 2 -H, 7 -H), (m, 16 H, 3-H aminophenyl, 5-H aminophenyl, H phenyl), 6.91 (d, J H-H =1.60 Hz, 2 H, 1-H, 8-H), 6.82 (d, J H-H = 7.59 Hz, 2 H, 1 -H, 8 - H) ppm. 13 C MR (101 MHz, CDCl 3, 25 C): δ = (q), (q), (q), (q), (q), (q), (q), (q), (phenyl), (2 -C, 7 -C), (3 -C, 6 - C), (2-C aminophenyl, 6-C aminophenyl), (3-C, 6-C), (phenyl, 1 -C), (phenyl), (phenyl), (1-C, 8-C), (4 -C, 5 -C), (4-C, 5-C), (C spiro) ppm. m/z (HRMS ESI + ): (M +. C 61 H 42 2 requires ), (M 2+. C 61 H 42 2 requires ). UV/Vis (CHCl 3 ): λ max (ε) = 372 nm (73020 mol -1 dm 3 cm -1 ). S3

4 2,2,7,7 -tetrakis-(4-(,-diphenylamino)phen-1-yl)-9,9 -spirobifluorene (3). In a Schlenk tube a stirred mixture of 2,2,7,7 -tetrabromo-9,9 -spirobifluorene (6) (153.1 mg, mmol), 4-(,diphenylamino)phenylboronic acid (315.5 mg, mmol), aqueous a 2 CO 3 2M (3 ml), Pd(PPh 3 ) 4 (60.9 mg, mmol) in dry THF (7 ml) was refluxed overnight under inert atmosphere. The grey precipitate formed was filtered over glass filter and washed with pentane (2 x 5 ml) to give the product (194.4 mg, 62%). 1 H MR (400 MHz, CDCl 3, 25 C): δ = 7.88 (d, J H-H = 7.95 Hz, 4 H, 4-H, 5-H, 4 - H, 5 -H), 7.59 (dd, J H-H = 7.99 Hz, J H-H = 1.68 Hz, 4 H, 3-H, 6-H, 3 -H, 6 -H), 7.32 (d, J H-H = 8.73 Hz, 8 H, 2-H phenyl, 6-H phenyl), (m, 16 H, H phenyl), (m, 36 H, 1-H, 8-H, 1 - H, 8 -H, 3-H phenyl, 5-H phenyl, H phenyl) ppm. 13 C MR (101 MHz, CDCl 3, 25 C): δ = (q), (q), (q), (q), (q), (q), (phenyl), (2-C phenyl, 6-C phenyl), (3-C, 6-C, 3 -C, 6 -C), (phenyl), (phenyl), (phenyl), (1- C, 8-C, 1 -C, 8 -C), (4-C, 5-C, 4 -C, 5 -C), (C spiro) ppm. m/z (HRMS ESI + ): (Ma +. C 97 H 68 4 a requires ). UV/Vis (CHCl 3 ): λ max (ε) = 373 (98400), 305 nm (48550 mol -1 dm 3 cm -1 ). (1) Saroja, G.; Pingzhu, Z.; Ernsting,. P.; Liebscher, J. J. Org. Chem., 2004, 69, (2) Yu, W.-L.; Pei, J.; Huang, W.; Heeger, A. J. Adv. Mater., 2000, 12, (3) Pei, J.; i, J.; Zhou, X.-H.; Cao, X.-Y.; Lai, Y.-H. J. Org. Chem., 2002, 67, S4

5 Figure S1. Current (black line) and ECL (red line) of 2. Pulse width: 0.3 s. S5

6 Figure S2. Coreactant ECL emission spectrum of 3 in DMF/0.1 M TBAH using 20 eq BPO. S6

7 Figure S3. PL emission spectra of 2 in 10-3 M DMF/0.1 M TBAH solution exciting at 370 nm (a) and 430 nm (b). S7

8 Figure S4. PL emission spectra of 1 (a) and 2 (b) in solid state. S8