Supporting Information for: ear Infrared Electrochromism in Electropolymerized Films of Biscyclometallated Ruthenium Complex Bridged by 1,2,4,5-Tetra(2-pyridyl)benzene Chang-Jiang Yao, Yu-Wu Zhong,, * Hai-Jing ie, Héctor D. Abruña, and Jiannian Yao, * Beijing ational Laboratory for Molecular Sciences, CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 119, People s Republic of China; Baker Laboratory, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, ew York 14853-131 --------------------------------------------------------------------------------------------------------- Correspondance: Prof. Yu-Wu Zhong CAS Key laboratory of photochemistry Institute of Chemistry, Chinese Academy of Sciences Beijing 119, China Email: zhongyuwu@iccas.ac.cn Website: http://zhongyuwu.iccas.ac.cn/ --------------------------------------------------------------------------------------------------------- List of contents: Synthesis of 2[PF 6 ] 2 --------------------------------------------------------------- Page S2-3 Electropolymerization of 2[PF 6 ] 2 ----------------------------------------------- Page S4-S7 XPS spectrum of a polymeric film of 2[PF 6 ] 2 on ITO glass ----------------- Page S8 S1
Synthesis of 2[PF 6 ] 2 tpb RuCl 3 AgOTf DMF/tBuOH Cl 3 Ru Ru Ru EtOH, reflux acetone 13 C (PF 6 ) 2 vtpy [2](PF 6 ) 2 To 4 ml of distilled ethanol were added vtpy 1 (1. mmol, 259 mg) and RuCl 3 3H 2 O (1. mmol, 261 mg). The mixture was refluxed for 4 h before cooling down to room temperature. The resulting precipitate was collected after filtration and washed successively with water and ether to afford Ru(vtpy)Cl 3 as a brown solid (46 mg, 87% yield) which was used in next transformation without further purification. To 4 ml of dry acetone were added Ru(vtpy)Cl 3 (.1 mmol, 47 mg) and AgOTf (.3 mmol, 78 mg). The reaction system was refluxed for 5 h before cooling down to room temperature. The mixture was filtered through celite and the filtrate was concentrated to dryness. To the residue were added 1,2,4,5-tetra(pyridin-2-yl)benzene 2 (tpb,.5 mmol, 19.3 mg), 12 ml DMF and 12 ml t-buoh. The mixture was bubbled with nitrogen for 2 min before the vial was capped and heated at 13 C for 48 h. After cooling to room temperature, the solvent was removed under reduced pressure and the residue was dissolved in 2 ml methanol. After adding an excess of KPF 6, the resulting precipitate was collected by filtering and washing with water and Et 2 O. The crude solid was purified by chromatography on silica gel to give 13 mg bisruthenium complex 2[PF 6 ] 2 as a black solid (eluent: CH 3 C/H 2 O/aq.KO 3 1/1/.1 black solid, 19% yield). Distinct 1 H MR spectrum (shown in the following page) could not be fully assigned due to signal broadening caused by contamination of small amount of mixed-valent complex, which contains paramagnetic Ru III species. MALDI-TOF m/z: 125 [M-PF 6 ] +, 115.2 [M-2PF 6 ] 2+ (The MS spectrum is shown in the following page). Anal. Calcd for C 6 H 42 F 12 1 P 2 Ru. 2 2H 2 O. Et 2 O: C, 51.7; H, 3.75;, 9.31. Found: C, 5.99; H: 3.48;, 9.12. 1 ie, H.-J.; Yao, J.; Zhong, Y.-W. J. Org. Chem. 211, 76, 4771. 2 Yao, C.-J.; Zhong, Y.-W.; Yao, J. J. Am. Chem. Soc. 211, 133, 15697 S2
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Electropolymerization of 2[PF 6 ] 2 All electrochemical experiment were carried out using a CHI62D potentiostat. All measurements were carried out in.1 M of Bu 4 ClO 4 /acetonitrile with a Ag/AgCl reference electrode. The working electrode is a glassy carbon, and a platinum coil is used as the counter electrode. A three-compartment electrochemical cell was used in electropolymerization experiments. The working electrode (ITO glass) was positioned parallel to and opposite the counter electrode. UV/vis/IR spectra were recorded using a PE Lambda 75 UV/vis/IR spectrophotometer. 2 1-1 -2-3 -1.8-1.6-1.4-1.2-1. -.8 E/V vs Ag/AgCl Figure S1. Reductive electropolymerization of 2 2+ (.6 mm in acetonitrile) on a Pt disk electrode (d = 2 mm) by 1 repeated potential scan cycles at 1 mv/s. Surface coverage = 5.7 1-1 mol/cm 2. S4
4 2-2 -4-6 -1.8-1.6-1.4-1.2-1. -.8 E/V vs Ag/AgCl Figure S2. Reductive electropolymerization of 2 2+ (.6 mm in acetonitrile) on a Pt disk electrode (d = 2 mm) by 2 repeated potential scan cycles at 1 mv/s. Surface coverage = 16 1-1 mol/cm 2. 8 4-4 -8-12 -1.8-1.6-1.4-1.2-1. -.8 E/V vs Ag/AgCl Figure S3. Reductive electropolymerization of 2 2+ (.6 mm in acetonitrile) on a Pt disk electrode (d = 2 mm) by 4 repeated potential scan cycles at 1 mv/s. Surface coverage = 3 1-1 mol/cm 2. S5
1-1 -2-1.8-1.6-1.4-1.2-1. -.8 V vs Ag/AgCl Figure S4. Reductive electropolymerization of 2 2+ (.6 mm in acetonitrile) on an ITO glass electrode (2 8 mm 2 ) by 1 repeated potential scan cycles at 1 mv/s. Surface coverage = 6.9 1-1 mol/cm 2. 4 2-2 -4-1.8-1.5-1.2 -.9 V vs Ag/AgCl Figure S5. Reductive electropolymerization of 2 2+ (.6 mm in acetonitrile) on an ITO glass electrode (2 8 mm 2 by 3 repeated potential scan cycles at 1 mv/s. Surface coverage = 5.5 1-9 mol/cm 2. S6
8 I/ A 4-4 -8-1.8-1.6-1.4-1.2-1. -.8 V vs Ag/AgCl Figure S6. Reductive electropolymerization of 22+ (.6 mm in acetonitrile) on an ITO glass electrode (2 8.5 mm2) by 6 repeated potential scan cycles at 1 mv/s. Surface coverage = 1 1-8 mol/cm2. 6 I/ A 3-3 -6-9 -1.8-1.6-1.4-1.2-1. -.8 V vs Ag/AgCl Figure S7. Reductive electropolymerization of 22+ (.6 mm in acetonitrile) on an ITO glass electrode (2 7 mm2) by 75 repeated potential scan cycles at 1 mv/s. Surface coverage = 1.3 1-8 mol/cm2. S7
XPS spectrum of a polymeric film of 2[PF 6 ] 2 on ITO glass X-ray photoelectron spectroscopy data were obtained with an ESCALab22i-XL electron spectrometer from VG Scientific using 3W AlKα radiation. The base pressure was about 3 1-9 mbar. The binding energies were referenced to the C1s line at 284.8 ev from adventitious carbon. Survey 1.8E+5 C1s+Ru3d 1.7E+5 1.6E+5 1.5E+5 1.4E+5 O1s Counts / s 1.3E+5 1.2E+5 1.1E+5 1.E+5 9.E+4 8.E+4 7.E+4 6.E+4 5.E+4 4.E+4 Ru3p3 1s 3.E+4 2.E+4 Cl2p 1.E+4.E+ 11 1 9 8 7 6 5 4 3 2 1 Binding Energy (ev) Figure S8. XPS spectrum of a polymeric film of [2](PF 6 ) 2. S8