Electronic Supporting Information

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1 Electronic Supporting Informtion Bright electrochemiluminescence of iridium(iii) complexes Klen N. Swnick, Sébstien Ldouceur, b Eli Zysmn-Colmn,* b nd Zhifeng Ding* Deprtment of Chemistry, The University of Western Ontrio, 1151 Richmond Street, London, Ontrio N6A 5B7, Cnd. Fx: ; Tel: x86161; E-mil: zfding@uwo.c b Déprtement de Chimie, Université de Sherbrooke, 2500 Blvd de l Université, Sherbrooke, Quebec J1K 2R1, Cnd. Fx: ; Tel: ; E-mil: Eli.Zysmn-Colmn@USherbrooke.c 1. Synthesis of [(C^N) 2 Ir(N^N)] + PF 6 Complexes 1-4 The synthesis nd chrcteriztion hve been published in previous report. 1 1

2 2. Electrochemicl nd Photophysicl Dt Summry A brief summry of the electrochemicl nd photophysicl dt is given below. Tble S1. Electrochemicl Properties of Compound E 1/2, ox E p E E 1/2, red E p V 69 mv 2.75 V V 78 mv V 84 mv 2.82 V V 84 mv V 105 mv 3.01 V V 69 mv V 96 mv 3.09 V V 75 mv Mesured in cetonitrile (c. 1.5 mm) with NBu 4 PF 6 (c. 0.1 M) s supporting electrolyte. Potentils (V) re reported vs. SCE stndrd electrode nd were clibrted using n internl stndrd Fc/Fc + redox couple (0.40 V in ACN). 2 Tble S2. Photophysicl Properties of Compound Photoluminescence (PL, mx ) PL Quntum yield ( ) b nm nm nm nm 79.7 Mesured in cetonitrile t 298 K. b Mesured t 298 K using Ru(bpy) 3 (PF 6 ) 2 = 9.5 % 3 in cetonitrile. 3. Generl Procedures for ECL Studies of Compounds 1-4 For nnihiltion ECL studies, pproximtely 2 mg of compound (1-4) ws dded to pyrex electrochemicl cell with flt Pyrex window t the bottom for detection of generted ECL, contining 0.1 M TBAPF 6 (tetrbutylmmonium hexfluorophosphte) supporting electrolyte in nhydrous cetonitrile (3 ml) tht ws ssembled in dry box. For corectnt studies, M BPO ws dded to the nnihiltion solution nd ssembled in dry box. A 2 mm dimeter Pt disc inlid in glss sheth were used s the working electrode (WE), coiled Pt wire s the counter electrode (CE), nd coiled Ag 2

3 wire s the qusi reference electrode (RE), respectively. Routine clening procedures for the electrodes nd cell were reported elsewhere. 4, 5 For detiled electrochemicl worksttion nd ECL setup informtion, plese refer to our previous publictions. 4, 5 In brief, the cyclic voltmmetry ws conducted on CHI 610A electrochemicl nlyzer (CH Instruments, Austin, TX). The experimentl prmeters for cyclic voltmmogrms (CVs) re listed here: V initil potentil in experimentl scle, positive or negtive initil scn polrity, 0.1 Vs scn rte, 4 sweep segments, V smple intervl, 2 s quiet time, AV sensitivity. Potentils (V) were clibrted using n internl stndrd Fc/Fc + redox couple (0.40 V in ACN) 2 fter ech experiment, nd re reported vs. SCE stndrd electrode. The ECL dt long with CV dt were obtined using the CHI 610A coupled with photomultiplier tube (PMT, R928, Hmmtsu, Jpn) held t -750 V with high voltge power supply. The ECL collected by the PMT under the flt Pyrex window t the bottom of the cell ws mesured s photocurrent, nd trnsformed to voltge signl, using picommeter/voltge source (Keithley 6487, Clevelnd, OH). The potentil, current signls from the electrochemicl worksttion, nd the photocurrent signl from the picommeter were sent simultneously through DAQ bord (DAQ 6052E, Ntionl Instruments, Austin, TX) in computer. The dt cquisition system ws controlled from custom-mde LbVIEW progrm (ECL_PMT610.vi, Ntionl Instruments, Austin, TX). The photosensitivity on the picommeter ws set mnully in order to void the sturtion. ECL pulsing experiments were conducted by using potentiostt (Model AFCBPI, Pine Instrument Co., Grove City, PA), n EG&G PAR 175 Universl Progrmmer (Princeton Applied Reserch, Trenton, NJ), nd the PMT with the picommeter in the similr mnner. The ssembly ws ble to perform the pulsing experiments without dely in reltive fst time pce. The dt cquisition for the current, potentil nd ECL signls ws crried out using nother homemde LbVIEW progrm (ECL_PAR610.vi). For corectnt systems, the pplied potentil ws pulsed t the WE in the cthodic region (in the experimentl potentil scle between 0 nd low 3

4 limit potentil vlue for the compound reduction s obtined from CV experiments) with pulse width of 0.1 s or 10 Hz. The ECL spectr were obtined by replcing the PMT with spectrometer (Cornerstone 260, Newport, Cnd) ttched to CCD cmer (Model DV420-BV, Andor Technology, Belfst, UK). The cmer ws cooled to -55 C prior to use, nd controlled by computer for opertion nd dt cquisition. The intensities versus wvelengths (spectr) were recorded by Andor Technology progrm. Similr to the pulsing experiments, the smples were pulsed t 10 Hz within ech compound s potentil window. ECL quntum efficiencies (QE) were clculted reltive to [Ru(bpy) 3 ](PF 6 ) 2 tken s 100% in cetonitrile solution (bsolute quntum ECL efficiency of [Ru(bpy) 3 ] 2+ is , 7 ) by integrting both the ECL intensity nd current vlue versus time for ech compound, s described in Eqution (S1), x = 100 æ è b ò b ö ò ECLdt Currentdt ø x æ è b ò b ö ò ECLdt Currentdt ø st (S1) where x stnds for the compound (1-4) nd st represents [Ru(bpy) 3 ](PF 6 ) 2. 4

5 4. Supplementry Cyclic Voltmmetry Dt Fig. S1 CV of 4 with vrying scn rte from 0.06 V/s to 0.18 V/s. Fig. S2 CV of [Ru(bpy) 3 ](PF 6 ) 2 with vrying scn rte from 0.04 V/s to 0.20 V/s. 5

6 Fig. S3 Plot of nodic pek current, i p, of 4 ginst 1/2 ( = scn rte). Fig. S4 Plot of cthodic pek current, i pc, of 4 ginst 1/2 ( = scn rte). 6

7 Fig. S5 Plot of nodic pek current, i p, of [Ru(bpy) 3 ](PF 6 ) 2 ginst 1/2 ( = scn rte). Fig. S6 Plot of cthodic pek current, i pc, of [Ru(bpy) 3 ](PF 6 ) 2 ginst 1/2 ( = scn rte). 7

8 5. Cyclic Voltmmogrms nd ECL-Voltge Curves in the Corectnt Pth Fig. S7 Cyclic voltmmogrms (dotted lines) overlid with the ECL-voltge curves (solid lines) of compounds 1-4 in the corectnt pth. 6. Supplementry Video nd Photogrph Plese see the ttched video in the ESI of complex 3 emitting green electrochemiluminescence when pulsing between its oxidtion nd reduction potentils t the working electrode. In ddition, plese refer to the photogrph of the ECL cell with complex 3 in solution under UV illumintion. 8

9 References 1. S. Ldouceur, D. Fortin nd E. Zysmn-Colmn, Inorg. Chem., 2011, 50, N. G. Connelly nd W. E. Geiger, Chem. Rev., 1996, 96, H. Ishid, S. Tobit, Y. Hsegw, R. Ktoh nd K. Nozki, Coord. Chem. Rev., 2010, 254, C. Booker, X. Wng, S. Hroun, J. Zhou, M. Jennings, B. L. Pgenkopf nd Z. Ding, Angew. Chem. Int. Ed., 2008, 47, K. N. Swnick, D. W. Dodd, J. T. Price, A. L. Brzeu, N. D. Jones, R. H. E. Hudson nd Z. Ding, Phys. Chem. Chem. Phys., 2011, 13, P. McCord nd A. J. Brd, J. Electronl. Chem., 1991, 318, J. E. Brtelt, S. M. Drew nd R. M. Wightmn, J. Electrochem. Soc., 1992, 139,

Supporting Information for A potential-controlled switch on/off mechanism for selective excitation in mixed electrochemiluminescent systems

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